TWI633932B - Multivalence photocatalytic heterogeneous materials for semiconductors - Google Patents

Abstract

The present invention describes a heterogeneous material comprising a p-type semiconductor having two metal oxides of two different oxidation states of the same metal, and n having a valence band deeper than the valence band of the p-type semiconductor A type semiconductor in which semiconductor types are in ion communication with each other. Heterogeneous materials enhance photocatalytic activity.

Description

Multivalent photocatalytic heterogeneous materials for semiconductors

The present disclosure describes a heterogeneous material having a p-type semiconductor comprising a mixed valence oxygen compound and an n-type semiconductor having a deeper valence band than the p-type semiconductor, and a mixed valence oxide compound ionic charge of the n-type semiconductor and the p-type semiconductor Ionic charge communication. These multivalent heterogeneous materials can be used to enhance the photocatalytic activity of photocatalytic materials.

Visible light activated photocatalysts can be configured for self-cleaning, air and water purification, as well as a variety of other interesting applications, often without the cost of non-renewable energy after deployment. This is because the photocatalyst can decompose contaminants (such as dyes, volatile organic compounds, and nitrogen oxides (NO _x )) by using an ambient light source such as solar radiation or indoor and outdoor light sources. Non-UV indoor light sources (such as light-emitting diodes and organic light-emitting diodes) are rapidly spreading as expected, and it is imperative to find ways to deploy visible light-activated photocatalysts for indoor applications, for example, cleaning household, public, and commercial locations. Indoor air, especially in confined areas such as airplanes, public buildings, etc. What's more, the additional applications of antimicrobial surfaces and self-cleaning materials are widely used in catering services, transportation, health care and hoteliers.

The elemental copper and copper compositions, alone or in combination with metal oxides, are described as useful photocatalytic/antibacterial/antiviral materials. Reference is made to U.S. Patent Publication Nos. 2007/0154561, 2009/0269269, 2011/0082026 and 2012/0201714; and with reference to Qiu Xiaoqing et al., "Mixed copper oxide/TiO2 nanocomposites in indoor environments as materials for risk reduction", American Chemical Society NanoJournal, 2012, Volume 6 (2), pp. 1609-1618 (Qiu, Xiaoqing et al ., "Hybrid CuxO/TiO ₂ Nanocomposites as risk-reduction materials in indoor environments," ACS Nano , 6(2) :1609-1618 (2012)). However, elemental copper is believed to be a general application environment due to the oxidation of elemental copper which simultaneously exhibits a decrease in antibacterial activity over time (durability) and an unattractive change in the decorative appearance surface (from copper metal to black copper oxide). Thus, it is necessary to increase the life expectancy of antimicrobial activity under time lapse. Thus, there is a need for a photocatalytic material that provides antimicrobial/antiviral activity without a change in decorative appearance that is unattractive.

The present disclosure describes a heterogeneous material having a p-type semiconductor comprising a mixed valence oxidized compound and an n-type semiconductor having a valence band deeper than the valence band of the p-type semiconductor, wherein the semiconductor is ionic charge each other Connected. These multivalent heterogeneous materials can be used to enhance the photocatalytic activity of the photocatalytic material and increase its durability (for example, maintaining photocatalytic activity over time). Photocatalytic materials are used to have and/or enhance antibacterial (light and dark) activity, antiviral activity, decomposition of volatile organic compounds (VOC) and/or discoloration of dyes in aqueous solutions.

Some embodiments comprise a heterogeneous material comprising: a p-type semiconductor comprising a first metal oxidizing compound and a second metal oxidizing compound, wherein the first metal oxidizing compound and the second metal oxidizing compound have different oxidations of the same metal And wherein the p-type semiconductor has a p-type valence band; and the n-type semiconductor has an n-type valence band deeper than the p-type valence band, wherein the n-type semiconductor is in ionic charge communication with the p-type semiconductor.

Another embodiment further comprises the noble metal being in ionic charge communication with the mixed valence oxidizing compound. In another embodiment, the precious metal is ruthenium, rhodium, palladium, silver, rhodium, platinum or gold. In another embodiment, the precious metal is supported on top of the n-type semiconductor.

Another embodiment further includes a second n-type semiconductor, wherein at least a portion of the second n-type semiconductor is ionically isolated from the mixed valence oxide compound. In another embodiment, the second n-type semiconductor comprises tantalum oxide. In another embodiment, the niobium oxide is CeO ₂ . In another embodiment, the second n-type semiconductor comprises a complex phase of TiO ₂ .

In another embodiment, the mixed valence oxidizing compound comprises a pair of identical metal chemical elements, such as copper, cobalt, manganese, iron, ruthenium, etc., in two different oxidation states, such as a combination of monovalent copper and divalent copper; a combination of divalent cobalt and trivalent cobalt; divalent manganese and trivalent manganese; divalent iron and ferric iron; or trivalent europium and tetravalent europium.

In another embodiment, the p-type semiconductor is loaded over the n-type semiconductor.

In another embodiment, the p-type semiconductor will be substantially uniformly dispersed over the n-type semiconductor. In another embodiment, the mixed valence oxidizing compound has a particle size of 100 nanometers or less.

In another embodiment, the monovalent copper and divalent copper compound are copper oxide (Cu _x O) compounds. In another embodiment, the copper oxide compound is chemically valence controlled. In another embodiment, the ratio of monovalent copper to divalent copper is between 10:90 and 90:10.

In another embodiment, the p-type semiconductor is a heterogeneous material of 0.001 to 10 The weight percentage and the n-type semiconductor are from 90 to 99.999 weight percent of the heterogeneous material.

The n-type semiconductor can be any suitable semiconductor wherein the charge carrier is an electron, such as an electron that is donated by a donor donor band in the conduction band. In another embodiment, the n-type semiconductor is an oxide comprising tantalum, tungsten, lanthanum, tin, zinc, lanthanum, zirconium, hafnium, indium, aluminum oxide. In another embodiment, the n-type semiconductor is Sn-Ti(O, C, N) ₂ , CeO ₂ , KTaO ₃ , Ta ₂ O ₅ , SnO ₂ , WO ₃ , ZnO, SrTiO ₃ , BaTiO ₃ , ZrTiO _{4 .} , In ₂ TiO ₅ , Al ₂ TiO ₅ or LiCa ₂ Zn ₂ V ₃ O ₁₂ . In another embodiment, the n-type semiconductor is Sn-Ti(O, C, N) ₂ . In another embodiment, the n-type semiconductor is Al _2-x In _x TiO ₅ , where 0 < x < 2. In another embodiment, the n-type semiconductor is Zr _1-y Ce _y TiO ₄ , where 0 < y < 1.

In another embodiment, the n-type semiconductor can comprise an oxide comprising titanium. In another embodiment, the oxide comprising titanium comprises a plurality of phases of titanium oxide. In another embodiment, the plurality of titanium oxides comprise a mixture of anatase phase TiO ₂ and rutile phase TiO ₂ .

In another embodiment, the n-type semiconductor is titanium oxide with dopants. By way of example, the dopant is capable of donating electrons to the conduction band of the titanium oxide. In another embodiment, the n-type semiconductor is titanium oxide doped with nitrogen, carbon, or both. In another embodiment, the n-type semiconductor is a titanium oxide comprising a compound represented by the chemical formula (Ti _1-r M _r )(O _2-st C _s N _t ), wherein: M represents tin, nickel, ruthenium, iridium , iron, ruthenium, vanadium, molybdenum, tungsten, zinc, copper or combinations thereof; r is in the range from 0 to 0.25; s is in the range from 0.001 to 0.1; and t is in the range from 0.001 to 0.1.

Another embodiment comprises a photocatalyst (Ti _0.99 Sn _0.01 ) (O _2-st C _s N _t ), (Ti _0.97 Sn _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Sn _0.05 ) (O _{2 ) -st} C _s N _t ), (Ti _0.90 Sn _0.10 )(O _2-st C _s N _t ), (Ti _0.85 Sn _0.15 )(O _2-st C _s N _t ), (Ti _0.985 Ni _0.015 )(O _2-st C _s N _t ), (Ti _0.98 Ni _0.02 ) (O _2-st C _s N _t ), (Ti _0.97 Ni _0.03 ) (O _2-st C _s N _t ), (Ti _0.99 Sr _0.01 ) ( O _2-st C _s N _t ), (Ti _0.97 Sr _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Sr _0.05 ) (O _2-st C _s N _t ), (Ti _0.97 Ba _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Ba _0.05 )(O _2-st C _s N _t ), (Ti _0.94 Sn _0.05F e _0.01 )(O _2-st C _s N _t ), (Ti _0.94 Sn _0.05 Ni _0.01 )(O _2-st C _s N _t ), (Ti _0.99 Fe _0.01 )(O _2-st C _s N _t ), (Ti _0.95 Zn _0.05 )(O _2-st C _s N _t ) (Ti _0.77 Sn _0.15 Cu _0.08 ) (O _2-st C _s N _t ), (Ti _0.85 Zn _0.15 ) (O _2-st C _s N _t ), (Ti _0.90 Bi _0.10 ) (O _2-st C _s N _t ), (Ti _0.996 V _0.004 ) (O _2-st C _s N _t ), (Ti _0.984 V _0.016 ) (O _2-st C _s N _t ), (Ti _0.970 V _0.03 ) (O _2-st C _s N _t ), (Ti _0.997 Mo _0.003 ) (O _2-st C _s N _t ), (Ti _0.984 Mo _0.016 ) (O _{2 -st} C _s N _t ), (Ti _0.957 Mo _0.043 ) (O _2-st C _s N _t ), (Ti _0.97 W _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 W _0.05 ) (O _2-st C _s N _t ), (Ti _0.996 V _0.004 ) (O _2-st C _s N _t ), (Ti _0.984 V _0.016 ) (O _2-st C _s N _t ), or (Ti _0.970 V _0.03 ) (O _2-st C _s N _t ).

Certain embodiments comprise a method of decomposing a chemical compound comprising exposing the chemical compound to a photocatalyst comprising a homogeneous material as described herein in the presence of light. In certain embodiments, the chemical compound is a contaminant, such as a volatile organic compound.

Some embodiments comprise a method of killing a microorganism comprising exposing the microorganism to a photocatalyst comprising a homogeneous material as described herein in the presence of light.

One particular embodiment as described herein comprises a method of loading a mixed valence compound. The method may comprise adding a dispersing agent to the mixed valence compound to make the surface of the n-type compound more positive; adding an attracting agent to the n-type compound to make the n-type semiconductor surface more negative; and doping at a lower than the mixed valence compound The temperature of the temperature is mixed with materials that are not the same as the charging.

10‧‧‧ Guide belt

20‧‧ ‧Price band

25‧‧ ‧ overlap

30‧‧ ‧Forbidden band

Fig. 1A is a diagram schematically showing the relationship between the conduction band of the metal material and the valence band.

Fig. 1B is a diagram schematically showing the relationship between the conduction band of the semiconductor material and the valence band.

Fig. 1C is a diagram schematically showing the relationship between the conduction band of the non-conductor material and the valence band.

Figure 2 is a schematic diagram showing the energy levels of the energy and energy bands of the various compounds described herein.

Figure 3 shows an X-ray diffraction pattern of an embodiment of the p-type and n-type composites described herein and a separate n-type material.

Figure 4 shows a separate X-ray diffraction pattern of another embodiment of the p-type and n-type composites described herein and the n-type material.

Figure 5 shows a separate X-ray diffraction pattern of another embodiment of the p-type and n-type composites described herein and the n-type material.

Figure 6 shows the diffuse reflectance spectra of the examples of p-type and n-type composites described herein compared to the n-type material alone (Ti(OCN) ₂ :Sn).

Figure 7 shows a diffuse reflectance spectrum of another embodiment of the p-type and n-type composites described herein compared to the n-type material alone (CeO ₂ ).

Figure 8 shows a diffuse reflectance spectrum of another embodiment of the p-type and n-type composites described herein compared to the n-type material alone.

Figure 9 shows a schematic representation of the decomposition of acetaldehyde of Ex-1A and CE-1 as described herein by various photocatalytic complexes.

Figure 10 shows the antibacterial activity (CFU/Specimen) of Escherichia coli after exposure to 800 lux visible light of a fluorescent lamp by various photocatalytic complexes of Ex-1A and CE-1 as described herein. Schematic diagram.

Figure 11 is a graph showing the antibacterial activity (colony forming unit/sample) of Escherichia coli after exposure to 800 lux of visible light of a fluorescent lamp by the various photocatalytic complexes of Ex-4 and CE-2 described herein.

Fig. 12A is a graph showing the durability of the enhanced antibacterial activity in Escherichia coli by the photocatalytic complex Ex-1 at 7 degrees Celsius and 85% relative humidity (RH).

Fig. 12B is a schematic view showing the durability of the enhanced antibacterial activity against Escherichia coli by the photocatalytic composite Ex-7 before and after treatment at 300 ° C for 20 minutes.

Figure 13 is a graphical representation showing the discoloration of the natural blue dyes by the various photocatalytic composites of Examples 1 and CE-1 as described herein and the rutile phase TiO ₂ in the presence or absence of Cu _X O loading.

Figure 14 shows a schematic representation of acetaldehyde decomposition by various photocatalytic complexes of Ex-12, Ex-13, Ex-15, Ex-16 and CE-6 as described herein.

Figure 15 shows a schematic representation of discoloration of dyes of blue dyes by Example 19 of different photocatalytic composites and no loading of SnO ₂ .

Figure 16 shows a schematic representation of the discoloration of natural blue dye by Example 18 of various photocatalytic composites.

Figure 17 shows the effect of the physical mixture CE-0 (0.25 wt.% CuO + 0.12 wt.% Cu ₂ O + 0.5 wt.% tin-doped Ti(OCN) ₂ photocatalyst) on the bactericidal properties of Escherichia coli. schematic diagram.

Figure 18 shows a schematic diagram of the effect of Ex-7A (0.5 wt.% Cu _X O loaded alumina (without photocatalyst)) on antimicrobial performance (E. coli sterilization study).

Fig. 19 is a view showing the effect of Ex-1B (0.5 wt.% Cu _X O-supported tin-doped Ti(OCN) ₂ photocatalyst) on antibacterial properties (Escherichia coli sterilization study).

Figure 20 is a schematic diagram showing the synergistic effect of Ex-1 (1 wt.% Cu _X O supported tin-doped Ti(OCN) ₂ ) on antimicrobial properties (E. coli sterilization study).

Fig. 21 is a view showing the results of enhanced durability of the antibacterial property of Ex-1 (1 wt.% Cu _X O-supported tin-doped Ti(OCN) ₂ ) (Escherichia coli sterilization study).

Figure 22 shows a schematic diagram of the synergistic effect of Cu _X O/P25 and Cu _X O/Al ₂ O ₃ on antimicrobial properties (E. coli sterilization study).

Fig. 23 is a view showing the results of enhanced durability of Cu _X O/P25 and Cu _X O/Al ₂ O ₃ in antibacterial properties (Escherichia coli sterilization study).

The present disclosure describes a heterogeneous material having a p-type semiconductor comprising a mixed valence oxidizing compound. The p-type semiconductor has a p-type valence band. The heterogeneous material also includes an n-type semiconductor having an n-type valence band with a deeper valence band than the p-type valence band. In the heterogeneous material, the n-type semiconductor is in ionic charge communication with the mixed valence oxidizing compound. These multivalent heterogeneous materials can be used to increase the photocatalysis of photocatalytic materials. It activates and enhances durability (i.e., increases photocatalytic activity over time). Photocatalytic materials are quite effective at having and/or enhancing antibacterial (light and dark) activity, antiviral activity, decomposition of volatile organic compounds (VOC), and/or discoloration of dyes in aqueous solutions.

As shown in Fig. 1, the conduction band 10 is a range of electron energy sufficient to free electrons from the atoms it bonds to move freely in the atomic lattice of the material, such as the same "delocalized electron". In semiconductors, the valence band 20 is the highest range of electron energy in which electrons normally exist at absolute zero. Valence electrons are essentially bonded to individual atoms, and to conductors that are more free to move in the atomic lattice of the material (present in the semiconductor). In the pattern of the electronic strip structure of the material, the valence band 20 is generally located below the conduction band and is separated from the conduction band by the energy gap 30 in the insulator and the semiconductor. In some materials, the conduction band does not substantially have a discernible energy gap that separates it from the valence band. For example, when the valence band energy is higher or less negative than the conduction band energy, the conduction band and the valence band may actually overlap (overlap 25).

A variety of materials can be classified by their energy gap; for example, by the difference between the valence band 20 and the conduction band 10. In a non-conductor (such as an insulator), the conduction band has a higher energy than the valence band, so for an insulator to exchange valence electrons for efficient conduction will consume too much energy. These insulators are said to have a non-zero energy gap. In the case of a conductor with many free electrons in a normal state, the conduction band 10 overlaps 25 and the valence band 20 has no energy gap, so it only needs to consume a little or no additional supply energy to exchange the valence electrons. . In semiconductors, the energy gap is small, on the order of 200 nm to 1000 nm. However, it is meant to be limited by theory, which is believed to be the reason for consuming relatively little energy (in the form of heat or light) to move the electrons of the semiconductor from the valence band to another energy level and to conduct electricity; therefore, it is called a semiconductor.

In certain embodiments, the heterogeneous material provides a p-type semiconductor comprising a mixed-valent oxidized compound having a p-type conduction band and a p-type valence band; and having a deeper, lower phase than the p-type valence band Another n-type semiconductor capable of, or more negative, n-type valence band. The n-type semiconductor should be in charge communication with the p-type semiconductor ion, meaning that the ionic charge can be transferred from the n-type semiconductor to the mixed-valent oxidized compound, or from the mixed-valent oxidized compound to the n-type semiconductor. Examples of suitable conduction and valence bands are shown in Figure 2. However, it is not intended to be limited by theory. If the valence band of the n-type semiconductor is deeper or more negative than the valence band of the p-type, the electrons are more easily transferred from the n-type to the p-type compound. If the material is ionically connected, electrons can pass from one compound to the next, and the high-priced compound can be regenerated into a low-cost complex. For example, Cu ²⁺ can be recovered as Cu ¹⁺ through this mechanism. In certain embodiments, the ionically connected materials will be loaded on top of each other. By loading, the material maintains its independent properties, such as Cu _X O (p-type semiconductor) separated from TiO ₂ , Ti(OCN) ₂ :Sn, etc. (n-type semiconductor). In a particular embodiment, a material is in contact with or adjacent to other materials on the surface, physically separated from other materials, and ionically separated or blended (physically mixed). In certain embodiments, such contact and/or separation can be determined by transmission electron microscopy (TEM) detection of p-type and n-type materials. In other embodiments, the heterogeneous material is integrated with the composite medium, such as incorporated into the compound/lattice.

The heterogeneous material can comprise any suitable p-type semiconductor, including any semiconductor in which the charge carrier is an efficient positive hole. These holes can exist in the p-type valence band, which can be filled with electrons, except for a few holes that can be essentially positively charged. In certain embodiments, the p-type semiconductor can comprise a mixed valence oxidizing compound having a p-type valence band. In certain embodiments, the mixed valence oxidizing compound comprises a mixed valence pair of the same metal elements, such as copper (I) and copper (II); cobalt (II) and cobalt (III); manganese (II) and manganese (III). Iron (II) and iron (III); and/or ruthenium (III) and (IV); and combinations thereof. In a particular embodiment, the copper (I) and copper (II) compounds can be Cu _X O compounds. In a particular embodiment, the mixed valence oxidizing compound can comprise Cu ¹⁺ and Cu ²⁺ . The ratio of the mixed valence oxidizing compound may be 10% to 90% to 90% to 10%. Specific ratios may also include: 15% to 85%; 20% to 80%; 25% to 75%; 30% to 70%; 35% to 65%; 40% to 60%; 45% to 55%; % to 50%; 55% to 45%; 60% to 40%; 65% to 35%; 70% to 30%; 75% to 25%; 80% to 20% and 85% to 15%.

In a particular embodiment, the ratio of Cu ¹⁺ :Cu ²⁺ of the mixed valence metal oxide compound is from 10% to 90% Cu ¹⁺ to 90% to 10% Cu ²⁺ . The ratio of Cu ¹⁺ :Cu ²⁺ may also be about 10%: 90% to about 30%: 70%, about 15%: 85% to about 25%: 75%, about 15%: 85%; about 20% : 80%; about 25%: 75%; about 30%: 70%; about 35%: 65%; about 40%: 60%; about 45%: 55%; about 50%: 50%; about 55%: 45%; about 60%: 40%; about 65%: 35%; about 70%: 30%; about 75%: 25%; about 80%: 20%; or about 85%: 15%. In certain embodiments, the ratio is the weight percent (wt%) of Cu ¹⁺ :Cu ²⁺ . In certain embodiments, the ratio is the molar percentage of Cu ¹⁺ :Cu ²⁺ .

In some embodiments, wherein the n-type semiconductor is in charge communication with the p-type semiconductor, the p-type semiconductor is supported on the n-type semiconductor. In some embodiments, wherein the n-type semiconductor is in charge communication with the p-type semiconductor, the p-type semiconductor can be embedded, stacked, contacted, and/or deposited on the n-type semiconductor. In certain embodiments, the p-type semiconductor mixed valence compound is substantially uniformly dispersed over the n-type semiconductor. The particle size of the mixed valence compound can be smaller than 200 nm; smaller than 190 nm; smaller than 180 nm; smaller than 170 nm; smaller than 160 nm; smaller than 150 nm; Nano is still small; smaller than 130 nm; smaller than 120 nm; smaller than 110 nm; smaller than 100 nm; smaller than 90 nm; smaller than 80 nm; Rice is still small; smaller than 60 nm; smaller than 50 nm; smaller than 40 nm; smaller than 30 nm; smaller than 20 nm; or smaller than 10 nm. In some characteristics In the examples, the mixed-valent compound has a particle diameter of 100 nm or less.

In certain embodiments, the p-type semiconductor comprises from 0.001 to 10 weight percent of the heterogeneous material and the n-type semiconductor comprises from 99.999 to 90 weight percent of the heterogeneous material. In further embodiments, the p-type semiconductor comprises 0.001 weight percent of the heterogeneous material; 0.005 weight percent of the heterogeneous material; 0.01 weight percent of the heterogeneous material; 0.05 weight percent of the heterogeneous material; heterogeneous 0.1% by weight of the material; 0.5% by weight of the heterogeneous material; 1% by weight of the heterogeneous material; 2% by weight of the heterogeneous material; 3% by weight of the heterogeneous material; 4% by weight of the heterogeneous material 5 wt% of the heterogeneous material; 6 wt% of the heterogeneous material; 7 wt% of the heterogeneous material; 8 wt% of the heterogeneous material; 9 wt% of the heterogeneous material; or, uneven 10% by weight of the phase material. In a further embodiment, the n-type semiconductor comprises 90 weight percent of the heterogeneous material; 91 weight percent of the heterogeneous material; 92 weight percent of the heterogeneous material; 93 weight percent of the heterogeneous material; heterogeneous 94% by weight of the material; 95% by weight of the heterogeneous material; 96% by weight of the heterogeneous material; 97% by weight of the heterogeneous material; 98% by weight of the heterogeneous material; 99% by weight of the heterogeneous material 99.1% by weight of heterogeneous material; 99.2% by weight of heterogeneous material; 99.3% by weight of heterogeneous material; 99.4% by weight of heterogeneous material; 99.5 weight% of heterogeneous material; Heterogeneous material 99.6 weight percent; 99.7 weight percent of the heterogeneous material; 99.8 weight percent of the heterogeneous material; or 99.5 weight percent of the heterogeneous material.

In certain embodiments, the p-type semiconductor comprises a mixture of copper oxide, such as a first copper oxide compound and a second copper oxide, such as a copper (I) compound (such as Cu ₂ O) and a copper (II) compound (such as Cu). ₂ O). In certain embodiments, the p-type semiconductor has a weight ratio by weight or a molar ratio of [earth(I) to copper (II)] of from about 1:9 to about 3:7, and about 1:3 to about A ratio of 1:6, or from about 1:3 to about 1:4, comprises copper (I) (such as Cu ₂ O) and copper (II) (such as Cu ₂ O).

Some embodiments include the p-type semiconductor and the n-type semiconductor combination of the preceding paragraph, the n-type semiconductor-based titanium oxide or tin-doped Ti(O, C, N) ₂ ), or titanium oxide, such as TiO ₂ , having More than one phase. In certain embodiments, such TiO ₂ has two phases, such as rutile phase TiO ₂ and anatase phase TiO ₂ . In certain embodiments, n is type semiconductor may be from about 70% to about 90% anatase phase and about 10% to 30% rutile TiO _2; from about 80% to about 90% anatase phase and 20% Up to about 30% rutile phase TiO ₂ ; about 75% to about 80% anatase phase and 15% to about 20% rutile phase TiO ₂ ; or about 83% anatase phase TiO ₂ and 17% rutile phase TiO ₂ . Some embodiments include a combination of a front-stage p-type semiconductor and an n-type semiconductor that is tin oxide.

Regarding a semiconductor comprising a p-type semiconductor having a mixture of copper oxide and Ti(O, C, N) _{2 which} is titanium oxide or tin-doped, or an n-type semiconductor having titanium oxide of not more than one phase, such as TiO ₂ , In certain embodiments, the copper oxide can be from about 0.1% to about 5%, from about 0.2% to about 2%, from about 0.2% to about 1.5%, about 0.5% or about, based on the total weight of the n-type and p-type semiconductors. 1%.

In some embodiments, the p-type semiconductor is loaded over the n-type semiconductor. In some embodiments, the n-type semiconductor is an element comprising tantalum, tungsten, tantalum, tin, zinc, lanthanum, zirconium, hafnium, indium or aluminum having a deeper valence band than the p-type semiconductor. Oxide. In some embodiments, the n-type semiconductor can be an anatase phase, a rutile phase, a wurtzite phase, a spinel, a perovskite, a burn. Pyrochlore, garnet, zircon and/or tialite phase materials or mixtures thereof. Each of these options is given the usual meaning as understood by one of ordinary skill in the semiconductor arts. The comparison of a given standard and the X-ray diffraction pattern of the generated sample is one of a number of methods that can be used to determine if the sample contains a particular phase. Example standards include diffraction by the National Institute of Standards and Technology (NIST) (Gaitherburg, Maryland, USA) and/or international diffraction. Information Center (ICDD, officially known as the Powder Diffraction Standards Joint Committee [JCPDS]) (International Centre for Diffraction Data (ICDD, formerly the Joint Committee on Powder Diffraction Standards [JCPDS]) (Newtown Square, Pennsylvania, USA)) X-ray diffraction pattern map provided. In certain embodiments, the perovskite mineral will be a perovskite oxide. In some embodiments, the perovskite oxide may comprise FeTiO ₃ , YFeO ₃ , LuRhO ₃ , BaSnO ₃ , Ba _0.8 Ca _0.2 TiO ₃ , CdSnO ₃ , LaRhO ₃ , LaRhO ₃ , LaMnO ₃ , CoTiO ₃ , CuTiO _{3 .} , MgTiO ₃ , ZnTiO ₃ , BiNb _1-x Ta _x O ₄ , wherein x=0 to 1.00, or InNb _1-x Ta _x O ₄ , wherein x=0 to 1.00.

In further embodiments, the n-type semiconductor may comprise germanium, tungsten, antimony, tin, zinc, antimony, zirconium, hafnium, indium, antimony, vanadium, iron, cadmium, antimony, and/or aluminum oxide. The n-type semiconductor may comprise CeO ₂ ; MgTa ₂ O ₆ ; BaTa ₂ O ₆ ; SrTa ₂ O ₆ ; Ta ₂ O ₅ ; FeTa ₂ O ₆ ; Hg ₂ Ta ₂ O ₇ ; Hg ₂ Nb ₂ O ₇ ; Hg ₂ TaVNb _1- VO7; K ₃ Ta ₃ Si ₂ O ₁₃ ; K ₂ LnTa ₅ O ₁₅ ; WO ₃ ; ZnO; SrTiO ₃ ; SrNb ₂ O ₇ ; SrTa ₂ O ₇ ; SrTaNbO ₇ ; Sr ₂ FeNbO ₆ ; Sr ₃ FeNb _{2 O 9; TiO 2; SnO 2} ; BaTiO 3; FeTiO 3; CdFe 2 O 4; MnTiO 3; Cs 2 Nb 4 O 11; KNbO 3; Sr 2 FeNbO 6; Sr 3 FeNb 2 O 9; NiNb 2 O 6; CoNb ₂ O ₆ ;ZnNb ₂ O ₆ ;Nb ₂ O ₅ ;K ₄ Nb ₆ O ₁₇ ;Rb ₄ Nb ₆ O ₁₇ ;CuTiO ₃ ;BiO ₃ ;In ₂ O ₃ ;LiTaO ₃ ;NiTiO ₃ ;In ₂ TiO ₅ Al ₂ TiO ₅ ; Al _2-x In _x TiO ₅ ; ZrTiO ₄ ; Zr _1-y Ce _y TiO ₄ ; LiCa ₂ Zn ₂ V ₃ O ₁₂ ; Cd ₂ SnO ₄ ; CdIn ₂ O ₄ ; Cd ₂ GeO _{4 ; Bi 2 W 2 O 9;} Bi 2 WO 6; Bi 3 TiNbO 9; ACrO 4, where A may be strontium, barium or combinations _{thereof; CuMnO 2; PbWO 4; CuFeO} 2; InVO 4; MVWO 6, wherein M Is Li, Ag or a combination thereof; Bi ₂ MNbO ₇ , wherein M can be aluminum, gallium, indium, antimony, rare earth, iron or a combination thereof; Zr ₂ WO ₆ ; PbWO ₄ ; SnW O ₄ ; Bi ₂ W ₂ O ₉ ; Na ₂ W ₄ O ₁₃ and/or MWO ₄ , wherein M may be calcium, zinc, copper or a combination thereof.

In some embodiments, the n-type semiconductor can be a vanadium garnet semiconducting photocatalyst. In certain embodiments, the vanadium garnet semiconducting photocatalyst can be represented by the formula (A _1-x O _x ) ₃ (M) ₂ (V ₃ )O ₁₂ wherein 0 < x < 1. In certain embodiments, the cumulative ion charge of (A _1-x O _x ) ₃ and (M) ₂ is +9. In some embodiments, A+ can be Li ⁺ , Cu ⁺ , Na ⁺ , K ⁺ , Ti ⁺ , Cd ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Y ³⁺ , Bi ³⁺ , Ln ³⁺ or a combination thereof. In certain embodiments, M can be Li ⁺ , Ni ²⁺ , Mg ²⁺ , Co ²⁺ , Cu ²⁺ , Zn ²⁺ , Mn ²⁺ , Cd ²⁺ , Cr ³⁺ , Fe ³⁺ or Sc One or any of ³⁺ or a combination thereof.

In some embodiments, the n-type semiconductor can be a vanadium garnet semiconducting photocatalyst. In certain embodiments, the vanadium garnet semiconducting photocatalyst can be represented by the formula 1: (A ²⁺ ) ₃ (M ⁺ M ²⁺ )(V ₃ )O ₁₂ . In certain embodiments, the vanadium garnet semiconductive photocatalyst can be Ca ₃ LiZnV ₃ O ₁₂ or Sr ₃ LiZnV ₃ O ₁₂ .

In some embodiments, the n-type semiconductor can be a mixed titanic acid. The term "mixed titanic acid" refers to a compound comprising titanium, oxygen, and at least one other element such as calcium, copper, magnesium or strontium. In certain embodiments, the mixed titanic acid can be CaCu ₂ Ti ₃ O ₁₂ (perovskite titanate); MgTi ₂ O ₅ (iron brookite); and/or La ₂ Ti ₂ O ₇ (green earth titanic acid). In certain embodiments, the titanium oxide may comprise a mixture of anatase and rutile phase of TiO _2.

In some embodiments, the n-type semiconductor can comprise a mixed copper oxide. Mixed copper oxide refers to an n-type semiconductor comprising copper, oxygen, and other elements distinct from copper and oxygen. In certain embodiments, the mixed copper oxide can be CuMnO ₂ or CuFeO ₂ .

In some embodiments, the n-type semiconductor can be a simple or mixed ferrite. In certain embodiments, the mixed ferrite may be α-Fe ₂ O ₃ ; MFe ₂ O ₄ , wherein M is magnesium, zinc, calcium, strontium or combinations thereof; Ca ₂ Fe ₂ O ₅ , MFe ₁₂ O ₁₉ Wherein M is ruthenium, osmium or a combination thereof; Sr ₇ Fe ₁₀ O ₂₂ , MFeO _2.5+x , wherein M is ruthenium, osmium or a combination thereof, Sr ₃ Fe ₂ O _6.16 ; Bi _1.5 Pb _0.5 Sr ₂ BiFe ₂ O _9.25 Pb ₂ Sr ₂ BiFe ₂ O _9+y ; Bi ₂ Sr ₂ BiFe ₂ O _9+y ; and/or Bi _1.5 Pb _0.5 Sr ₄ Fe ₂ O _10.04 .

In some embodiments, the n-type semiconductor can be a CuX supported oxynitride semiconducting photocatalyst. In certain embodiments, the oxynitride semiconducting photocatalyst can comprise TaON; MTaO ₂ N, wherein M is calcium, lanthanum, cerium or a combination thereof; SrNb ₂ O _7-x N _x ; (Ga _1-x Zn _x (N _1-x O _x ); and/or (Zn _1+x Ge)(N ₂ O _x ).

In some embodiments, the n-type semiconductor can be a CuX supported sulfide, selenide or sulphide selenide semiconductor photocatalyst. In certain embodiments, the sulfide, selenide or sulphide selenide semiconductor photocatalyst may comprise Cd(Sy, Se _1-y ), where 0 < y <1; (Cd, Zn(Sy, Se _1-y) ), where 0 < y <1; (AgIn) _x Zn ₂ ( _1-x ) (S _y , Se _1-y ) ₂ , where 0 < y <1; (CuIn) _x Zn ₂ ( _1-x ) ( S _y ,Se _1-y ) ₂ , where 0<y<1; (CuAgIn) _X Sn ₂ ( _1-x )(S _y , Se _1-y ) ₂ , where 0<y<1; and/or Sm ₂ Ti ₂ S ₂ O ₅ .

In a particular embodiment, the n-type semiconductor comprises a compound represented by the chemical formula "Al _2-x In _x TiO ₅ ", wherein x is in the range of 0 to 2 (0 < x < 2). In another specific embodiment, the n-type semiconductor comprises a compound represented by the chemical formula "Zr _1-y Ce _y TiO ₄ ", wherein y is in the range of 0 to 1 (0 < y < 1). In a particular embodiment, the n-type semiconductor is titanium oxide having a valence band controlled by doping. In certain embodiments, the n-type semiconductor is titanium oxide doped with nitrogen or carbon or both. In certain embodiments, the titanium oxide comprises a compound represented by the formula (Ti _1-r M _r )(O _2-st C _s N _t ), wherein M is tin, nickel, ruthenium, osmium, iron, ruthenium, vanadium , manganese, tungsten, zinc, copper or a combination thereof; r is in the range of 0 to 0.25; s is in the range of 0.001 to 0.1; and, t is in the range of 0.001 to 0.1. In certain embodiments, r cannot be greater than 0.2. In certain embodiments, r can be specifically 0; 0.01; 0.02; 0.03; 0.04; 0.05; 0.06; 0.07; 0.08; 0.09; 0.10; 0.11; 0.12; 0.13; 0.14; 0.15; 0.16; 0.17; 0.19; 0.20; 0.21; 0.22; 0.23; 0.24; or 0.25. In certain embodiments, s can be specifically 0.001; 0.005; 0.01; 0.02; 0.03; 0.04; 0.05; 0.06; 0.07; 0.08; 0.09 or 0.1. In certain embodiments, t can be specified to be 0.001; 0.005; 0.01; 0.02; 0.03; 0.04; 0.05; 0.06; 0.07; 0.08; 0.09 or 0.1.

This material is also described in the co-pending and co-assigned applications, Serial No. 13/741,191, filed on January 14, 2013, the entire application of which is incorporated by reference. In the description of the compound and / or composition. In certain embodiments, M is tin, nickel, ruthenium, osmium, iron, ruthenium or combinations thereof. In certain embodiments, r is in the range of 0.0001 to 0.15. In certain embodiments, M is tin. In certain embodiments, r is at least 0.001. In some embodiments, the n-type semiconductor comprises (Ti _0.99 Sn _0.01 ) (O _2-st CsN _t ), (Ti _0.97 Sn _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Sn _0.05 ) ( O _2-st C _s N _t ), (Ti _0.90 Sn _0.10 ) (O _2-st C _s N _t ), (Ti _0.85 Sn _0.15 ) (O _2-st C _s N _t ), (Ti _0.985 Ni _0.015 ) (O _2-st C _s N _t ), (Ti _0.98 Ni _0.02 ) (O _2-st C _s N _t ), (Ti _0.97 Ni _0.03 ) (O _2-st C _s N _t ), (Ti _0.99 Sr _0.01 (O _2-st C _s N _t ), (Ti _0.97 Sr _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Sr _0.05 ) (O _2-st C _s N _t ), (Ti _0.97 Ba _0.03 )(O _2-st C _s N _t ), (Ti _0.95 Ba _0.05 )(O _2-st C _s N _t ), (Ti _0.94 Sn _0.05 Fe _0.01 )(O _2-st C _s N _t ), ( Ti _0.94 Sn _0.05 Ni _0.01 )(O _2-st C _s N _t ), (Ti _0.99 Fe _0.01 )(O _2-st C _s N _t ), (Ti _0.95 Zn _0.05 )(O _2-st C _s N _t ), (Ti _0.77 Sn _0.15 Cu _0.08 ) (O _2-st C _s N _t ), (Ti _0.85 Zn _0.15 ) (O _2-st C _s N _t ), (Ti _0.90 Bi _0.10 ) (O _2-st C _s N _t ), (Ti _0.996 V _0.004 ) (O _2-st C _s N _t ), (Ti _0.984 V _0.016 ) (O _2-st C _s N _t ), (Ti _0.970 V _0.03 ) (O _2-st C _s N _t ), (Ti _0.997 MO _0.003 ) (O _2-st C _s N _t ), (Ti _0.984 MO _{0.0 16} ) (O _2-st C _s N _t ), (Ti _0.957 MO _0.043 ) (O _2-st C _s N _t ), (Ti _0.97 W _0.03 ) (O _2-st C _s N _t ), and/or (Ti _0.95 W _0.05 ) (O _2-st C _s N _t ). In some embodiments, the n-type semiconductor comprises (Ti _0.996 V _0.004 ) (O _2-st C _s N _t ), (Ti _0.984 V _0.016 ) (O _2-st C _s N _t ), and/or (Ti _0.970 V _0.03 ) (O _2-st C _s N _t ).

In some embodiments, wherein the heterogeneous material comprises a p-type semiconductor supported on the n-type semiconductor, the heterogeneous material further comprises a second n-type semiconductor, wherein at least a portion of the second n-type semiconductor and the p-type semiconductor ion Charge isolation. In some embodiments, at least a portion of the second n-type semiconductor can be physically separated from the p-type conductor, ionically separated, blended, and/or unsupported by the p-type semiconductor. In some embodiments, the second n-type semiconductor can be any of the n-type semiconductors described elsewhere in this application. In some embodiments, the ionic charge separating or blending the n-type semiconductor may comprise a CeO ₂ and/or a complex phase n-type semiconductor compound. In some embodiments, the complex phase n-type semiconductor compound comprises an anatase phase and a rutile phase compound. In some embodiments, the complex phase n-type semiconductor compound can be a titanium oxide. In some embodiments, the anatase phase can range from 2.5% to about 97.5%, from about 5% to about 95%, and/or from about 10% to about 90%, and the rutile phase can range from 97.5% to about 2.5%, 95% to about 5%, and/or from about 10% to about 90%. Non-limiting examples of suitable materials include, but are not limited to, a TiO ₂ mixture (83% anatase phase TiO ₂ + 17% rutile phase TiO ₂ ) sold under the brand name P25 by Evonik. In some embodiments, the n-type semiconductor physically mixed with the p-type supported on WO ₃ may comprise CeO ₂ , TiO ₂ , SrTiO _{3 ,} and/or KTaO ₃ . In some embodiments, an n-type semiconductor (eg, P25) physically mixed with a p-type supported on a complex phase n-type semiconductor compound may comprise an unsupported complex phase n-type semiconductor compound (eg, P25). In some embodiments, the n-type semiconductor physically mixed with the _p -type supported on the complex phase n-type semiconductor compound may comprise CeO ₂ , TiO ₂ , SrTiO _{3 ,} and/or KTaO ₃ . In some embodiments, the n-type semiconductor can be inorganic. In some embodiments, the inorganic n-type semiconductor can be an oxide such as a metal dioxide comprising CeO ₂ , TiO ₂ , or the like. In some embodiments, the n-type semiconductor may include SiO ₂ , SnO ₂ , Al ₂ O ₃ , ZrO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , NiO, Nb ₂ O ₅ , and or CeO ₂ .

In some embodiments, the n-type semiconductor can be RE _k E _m O _n , wherein RE is a rare earth element, E is an element or a combination of elements, O is oxygen, and 1 k 2,2 m 3, and 0 n 3. In some embodiments, the n-type semiconductor can be RE _p O _q , wherein RE is a rare earth metal element and p can be greater than or equal to 1, and less than or equal to 2, or can be between 1 and 2; and q can be greater than or equal to 2 is less than or equal to 3, or may be between 2 and 3. Examples of suitable rare earth elements include lanthanum, cerium and lanthanides and actinides. The lanthanide element contains an element having an atomic number of 57 to 71. The lanthanide element contains elements of atomic number 89 to 103. In certain embodiments, the n-type semiconductor can be Ce _x Zr _y O ₂ with a y/x ratio = 0.001 to 0.999. In some embodiments, the n-type semiconductor can be germanium. In some embodiments, the n-type semiconductor can be CeO _a (a 2). In certain embodiments, the n-type semiconductor can be a cerium oxide (CeO ₂ ).

In some embodiments, the n-type semiconductor can be a non-oxide. In certain embodiments, the non-oxide can be a carbide and/or a nitride. In certain embodiments, the carbide can be tantalum carbide.

In some embodiments, the molar ratio of the physical mixture of the n-type semiconductor (such as CeO ₂ ) and the p-type semiconductor supported by WO ₃ (eg, Cu _X O-WO ₃ ) may be 0% of the n-type semiconductor - 100%-1% of 99% and p-type semiconductors (Cu _x O supported at WO ₃ ) In certain embodiments, a physical mixture of an n-type semiconductor (such as CeO ₂ ) and a p-type semiconductor supported on WO ₃ 75 to 25% molar ratio may be 25% to 75% n-type semiconductor (and every integer between these) to a load n-type material (e.g., WO ₃₎ of the p-type semiconductor (between this and the Every integer). In some embodiments, the molar ratio of the physical mixture of the n-type semiconductor (such as CeO ₂ ) and the p-type semiconductor supported by WO ₃ may be 40% to 60% of the n-type semiconductor (between and An integer) from 60% to 40% of the p-type semiconductor loaded with an n-type material (such as WO ₃ ) (with each integer between them).

In certain embodiments, the heterogeneous material may further comprise a noble metal in charge communication with the mixed valence oxidizing compound ion. In some embodiments, the precious metal element is supported on the n-type semiconductor. In some embodiments, the noble metal can be, but is not limited to, ruthenium, rhodium, palladium, silver, rhodium, platinum, and/or gold or mixtures thereof. In one embodiment, the precious metal is platinum.

In certain embodiments, a method for loading a mixed valence compound can add a p-type precursor to an attractant to make the surface charge of the n-type semiconductor more negative, wherein the p-type precursor comprises a copper cation complex. In some embodiments, a method for supporting a mixed valence compound can include adding an attractant to an n-type compound; and combining the n-type and p-type precursors with each other at a temperature lower than a doping temperature of the mixed-valent compound. In certain embodiments, the method further comprises the step of adding a dispersant to the n-type compound to make the surface charge of the n-type compound more positive.

In some embodiments, a method for supporting a mixed valence compound may add a dispersing agent to the n-type compound to make the surface of the n-type compound more positively charged; and add a p-type precursor to the dispersing agent and the n-type compound, wherein The p-type precursor comprises a copper cation complex; an attractant is added to the n-type compound to make the n-type semiconductor surface charge more negative; and a dissimilar charge material is bonded to each other at a temperature lower than the doping temperature of the mixed valence compound. .

In certain embodiments, the dispersing agent can be a strong acid. In certain embodiments, the dispersing agent can be 4-7 molar concentrations (M) of hydrochloric acid. In certain embodiments, the dispersing agent is 6M hydrochloric acid.

In some methods, the monovalent control material is added separately to the dissimilar loading material to control the mixed valence oxide during the synthesis of the mixed valence oxide. In certain embodiments, the valence control material is a mild reducing agent. In certain embodiments, the valence controlling material can be at least one of a sugar, a hydrazine, an amino acid, and/or a guanamine. In certain embodiments, the guanamine can be urea. In certain embodiments, the saccharide can be sucrose, fructose, and/or glucose. In certain embodiments, the saccharide can be glucose. In certain embodiments, the moss is Carbohydrazide, Oxalyl Dihydrazide, Maleic Hydrazide, Diformyl Hydrazine, or Tetramethylhydrazine. Tetraformyl Trisazine. In certain embodiments, the amino acid is at least one of a proprotein or a natural amino acid. In certain embodiments, the amino acid can be an aliphatic amino acid (such as glycine, alanine, valine, leucine, and/or isoleucine). In certain embodiments, the amino acid can be a hydroxyl or sulfur containing amino acid (such as serine, cysteine, threonine, and/or methionine). In certain embodiments, the amino acid can be a ring (such as valine). In certain embodiments, the amino acid can be an aromatic ring (such as phenylalanine, tyrosine, and/or tryptophan). In certain embodiments, the amino acid can be basic (eg, histidine, lysine, and/or arginine). In certain embodiments, the amino acid can be acidic or a guanamine (such as aspartic acid, sitamine, aspartame, and/or glutamic acid). In certain embodiments, the amino acid is selenocysteine and/or pyrrolysine. In certain embodiments, the amino acid can be non-proteinogenic. In certain embodiments, the non-proteinogenic amino acid comprises no such found in the protein (for example, carnitine, GABA). In certain embodiments, the non-proteinogenic amino acid can be subjected to standard cellular mechanisms (standard cellular Amino acids (such as hydroxyproline and selenomethionine) separated by machinery. In certain embodiments, the amino acid is water soluble. In certain embodiments, the amino acid is soluble in water at 90 degrees Celsius. In certain embodiments, the amino acid is substantially completely soluble in water at 90 degrees Celsius. The term "soluble" has its ordinary meaning as known to those of ordinary skill in the art.

In some embodiments, the ratio of mixed valence oxidizing compounds, such as Cu ⁺ compounds and Cu ²⁺ compounds, can be regulated by a method of loading copper onto a p-type semiconductor, the method comprising the addition of an attractant. In certain embodiments, the attractant that can control the ratio of the mixed valence oxide can comprise a monosaccharide and a base compound. In certain embodiments, the monosaccharide is glucose. In certain embodiments, the glucose can be D-glucose and/or L-glucose. In certain embodiments, the ratio of glucose to NaOH above may range from 10% to 90% to 90% to 10%. Specific ratios may also include: 15% to 85%; 20% to 80%; 25% to 75%; 30% to 70%; 35% to 65%; 40% to 60%; 45% to 55%; % to 50%; 55% to 45%; 60% to 40%; 65% to 35%; 70% to 30%; 75% to 25%; 80% to 20%; and 85% to 15%. In certain embodiments, the base is NaOH. Cu _x O compounds are valence control chemicals.

In certain embodiments, the attractant can be an agent that provides an effective amount of hydroxide ions such that the pH of the total solution is between 8.0 and 9.0. In certain embodiments, the attractant can be a strong base. In certain embodiments, the attractant is a strong base at a concentration of 4-7 moles. In certain embodiments, the attractant is NaOH at a concentration of 6 moles.

In certain embodiments, the p-type leader can be a compound that is substantially sodium-free. In certain embodiments, the substantially sodium-free compound can be a copper cationic complex. In certain embodiments, the copper cation complex may be Bis(Ethylenediamine)Copper(II)(BEDCull), divalent copper tetraammonium chloride (Copper(II) Tetramine chloride), copper (II) tetra amine sulfate, and/or copper (II) tetra amine hydroxide and/or mixtures thereof . In certain embodiments, the compound can be bis(ethylenediamine hydroxide) copper (II). The structure of BEDCull is shown below:

In certain embodiments, the mixed valence compound has a doping temperature between 150 and 700 degrees Celsius. In certain embodiments, the doping temperature of the compound less than the mixed valence is less than 175 degrees Celsius, less than 150 degrees Celsius, and less than 125 degrees Celsius. In certain embodiments, the mixing temperature is between 75 and 125 degrees Celsius. In certain embodiments, the mixing temperature is 80 degrees Celsius; 85 degrees Celsius; 95 degrees Celsius; 100 degrees Celsius; 105 degrees Celsius; 110 degrees Celsius; 115 degrees Celsius; 120 degrees Celsius; or 120 degrees Celsius.

In certain embodiments, the precursors selected for the p-type semiconductor can be chlorides, acetates, nitrates, sulfates, carbonates, oxides, hydroxides, salts of peroxides, or combinations thereof.

In certain embodiments, the heterogeneous material has photocatalytic activity. The heterogeneous material may be antibacterial (light and dark); antiviral; may decompose volatile organic compounds; and/or may discolor the food with an additive dye. Non-limiting examples of suitable food additive dyes include natural blue powder (Color Maker, Anaheim, CA, USA) (Color Maker, Anaheim, California, USA) and/or FD&C Blue No. 2 synthetic food. A dye (synthetic blue powder, Chromatech, Michigan, USA) (Synthetic blue colored powder, Chromatech, Inc., Michigan, USA) was added. The heterogeneous materials described here can also increase the photocatalytic material. Durability of the material (effectiveness time).

One of ordinary skill in the art recognizes methods for determining whether a heterogeneous material is antibacterial (light) or not, for example, after exposing a heterogeneous material to visible light. In one embodiment, the antimicrobial exposure results in at least a 10% reduction (90% remaining), at least a 50% reduction (50% remaining), at least a 99% reduction (at least 1% remaining), at least a reduction 99.9% (at least 0.1% remaining) or at least 100% reduction (0% remaining). An example of determining whether the heterogeneous material is antibacterial (light) can be obtained by assessing the amount of viable bacteria; for example, how much the survival of the bacteria is reduced after exposure of the heterogeneous material to the bacteria and exposure to visible light. By way of example, the amount of viable bacteria in the sample can be assessed after exposing the sample for a predetermined period of time. In certain embodiments, the sample can be exposed for 15 minutes, 30 minutes, 1 hour, 2 hours, 5 hours, 7.5 hours, 10 hours, 12 hours, or 24 hours. In certain embodiments, the sample is exposed to a 800 lux fluorescent source or to a blue light emitting diode of at least 5 mW/cm ² .

One of ordinary skill in the art recognizes methods for determining whether a heterogeneous material is antibacterial (dark). In one embodiment, the antimicrobial exposure results in at least a 10% reduction (90% remaining), at least a 50% reduction (50% remaining), at least a 99% reduction (at least 1% remaining), at least 99.9 % reduction (at least 0.1% remaining) or at least 100% reduction (0% remaining). An example of determining whether a heterogeneous material is antibacterial (dark) can be obtained by assessing the amount of viable bacteria, such as the number of viable colonies that are reduced or decreased after the heterogeneous material is contacted with the bacteria and not exposed to visible light.

One of ordinary skill in the art recognizes methods for determining whether a heterogeneous material is antiviral. In one example, determining whether a heterogeneous material is antiviral can be assessed by, for example, inhibiting or reducing the number of viral (phage) colonies. In one embodiment, determining whether the heterogeneous material is antiviral can be calculated by calculating the amount of viral colonies present over time after exposure to the heterogeneous material. In an embodiment, Antiviral exposure results in at least a 10% reduction (90% remaining), at least a 50% reduction (50% remaining), at least a 99% reduction (at least 1% remaining), at least 99.9% reduction (at least 0.1% remaining) ) or at least 100% reduction (0% remaining).

One of ordinary skill in the art recognizes methods for determining whether a heterogeneous material can decompose a volatile organic compound. An example of determining whether the heterogeneous material decomposes a volatile organic compound can be evaluated by measuring the degradation of the organic compound under electromagnetic radiation such as visible light. In one embodiment, determining the percentage of acetaldehyde degradation to reduction or initial degradation is an option to determine the decomposition of volatile organic compounds; for example, ranging from 0% to 90% over time; or 270 mW to visible light. /cm2 power of 455 nm blue light emitting diode under 3 to 10 hours or 5 hours. In certain embodiments, the degradation is at least 50%, 60%, 70%, 80%, 90%, or 100% of the initial value of acetaldehyde after exposure to the heterogeneous material.

One of ordinary skill in the art recognizes methods for determining whether a heterogeneous material discolors a food additive or dye. An example of determining the discoloration of a food additive may be a reduction in the amount of dye added by food over time or a percentage of the initial amount. In one embodiment, the food addition may be a natural anthocyanin food additive dye or an FDC food additive. In certain embodiments, the discoloration of the food dye additive can range from 0% to 60% after 5 hours of exposure to a blue light emitting diode having a power of 45 mW/cm2 to 455 nm. In certain embodiments, the degradation is at least 25%, 30%, 40%, 50%, and/or 60% of the initial amount of the natural anthocyanin food additive dye after exposure to the heterogeneous material.

One of ordinary skill in the art recognizes methods for determining whether a heterogeneous material maintains activity over time, such as the durability of a heterogeneous material. In some embodiments, the color change added by the food dye is reduced from 0% to 60% after 5 hours of exposure to a blue light emitting diode having a power of 45 mW/cm2 at 455 nm. for example, In certain embodiments, the antimicrobial activity will remain for at least 7 days after exposure to 85% relative humidity and 85 degrees Celsius, an exemplary but non-limiting embodiment such as:

Embodiment 1: A heterogeneous material comprises: a p-type semiconductor comprising a first metal oxidizing compound and a second metal oxidizing compound, wherein the first oxidizing compound and the second oxidizing compound have different oxidation states of the same metal And wherein the p-type semiconductor has a p-type valence band; and the n-type semiconductor, the n-type semiconductor has an n-type valence band deeper than the p-type valence band, wherein the n-type semiconductor is in charge communication with the p-type semiconductor ion.

Embodiment 2: The heterogeneous material of Embodiment 1, further comprising a noble metal in charge communication with the first metal oxidizing compound and the second metal oxidizing compound ion.

Embodiment 3: The heterogeneous material of Embodiment 2, wherein the noble metal is ruthenium, rhodium, palladium, silver, rhodium, platinum or gold.

Embodiment 4: The heterogeneous material of Embodiment 2 or 3, wherein the precious metal is supported on the n-type semiconductor.

Embodiment 5: The heterogeneous material of Embodiment 1, 2, 3, or 4, further comprising a second n-type semiconductor, wherein at least a portion of the second n-type semiconductor is ionically isolated from the p-type semiconductor.

Embodiment 6: The heterogeneous material of Embodiment 5, wherein the second n-type semiconductor comprises a cerium oxide.

Embodiment 7: The heterogeneous material of Embodiment 6, wherein the cerium oxide is CeO ₂ .

Embodiment 8: The heterogeneous material of Embodiment 5, wherein the second n-type semiconductor comprises a complex phase TiO ₂ .

Embodiment 9: The heterogeneous material of Embodiment 1, 2, 3, 4, 5, 6, 7, or 8, wherein the first metal oxide compound comprises copper (I) and the second metal oxide compound comprises copper (II) The first metal oxidizing compound comprises cobalt (II) and the second metal oxidizing compound comprises cobalt (III); the first metal oxidizing compound comprises manganese (II) and the second metal oxidizing compound comprises manganese (III); the first metal oxidizing compound The iron-containing (II) and second metal oxidizing compound comprise iron (III), or the first metal oxidizing compound comprises cerium (III) and the second metal oxidizing compound comprises cerium (IV).

Embodiment 10: The heterogeneous material of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the p-type semiconductor is loaded over the n-type semiconductor.

Embodiment 11: The heterogeneous material of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the p-type semiconductor is substantially uniformly dispersed over the n-type semiconductor.

Embodiment 12: The heterogeneous material of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, wherein the p-type semiconductor is a pellet having 100 nm or less The particle form of the diameter.

Embodiment 13: The heterogeneous material of Embodiment 9, wherein the p-type semiconductor comprises copper (I) and copper (II).

Embodiment 14: The heterogeneous material of Embodiment 13, wherein the p-type semiconductor comprises Cu _x O.

Embodiment 15: The heterogeneous material of Embodiment 14, wherein the CuxO is chemically valence controlled.

Embodiment 16: A heterogeneous material as in Example 9, wherein copper (I): copper (II) The ratio is between 10:90 and 30:70.

Embodiment 17: Heterogeneous material as in Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the p-type semiconductor is non- 0.001 to 10 weight percent of the homogeneous material, and the n-type semiconductor is 90 to 99.999 weight percent of the heterogeneous material.

Embodiment 18: Heterogeneous material as in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the n-type semiconductor It is an oxide of bismuth, tungsten, bismuth, tin, zinc, antimony, zirconium, hafnium, indium, or aluminum.

Embodiment 19: Heterogeneous material as in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the n-type semiconductor Containing Sn-Ti(O,C,N) ₂ , MgTi ₂ O ₅ , CeO ₂ , KTaO ₃ , Ta ₂ O ₅ , SnO ₂ , WO ₃ , ZnO, SrTiO ₃ , BaTiO ₃ , ZrTiO ₄ , In ₂ TiO ₅ , Al ₂ TiO ₅ or LiCa ₂ Zn ₂ V ₃ O ₁₂ .

Embodiment 20: Heterogeneous material as in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the n-type The semiconductor is Al _2-x In _x TiO ₅ , where 0 < x < 2.

Embodiment 21: Heterogeneous material as in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the n-type semiconductor Is Zr _1-y Ce _y TiO ₄ , where 0 < y < 1.

Embodiment 22: Heterogeneous material as in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the n-type semiconductor It is a titanium oxide having a valence band regulated by doping.

Embodiment 23: Heterogeneous material as in Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the n-type semiconductor It is titanium oxide doped with nitrogen, carbon or both.

Embodiment 24: The heterogeneous material of Embodiment 22, wherein the n-type semiconductor is titanium oxide, the oxidation Containing a compound represented by the chemical formula (Ti _1-r M _r )(O _2-st C _s N _t ), wherein: M represents tin, nickel, ruthenium, osmium, iron, ruthenium, vanadium, molybdenum, tungsten, zinc, copper Or a combination thereof; r from 0 to 0.25; s from 0.001 to 0.1; and t from 0.001 to 0.1.

Embodiment 25: The heterogeneous material as in Example 24, comprising (Ti _0.99 Sn _0.01 ) (O _2-st C _s N _t ), (Ti _0.97 Sn _0.03 ) (O _2-st C _s N _t ), ( Ti _0.95 Sn _0.05 )(O _2-st C _s N _t ), (Ti _0.90 Sn _0.10 )(O _2-st C _s N _t ), (Ti _0.85 Sn _0.15 )(O _2-st C _s N _t ), (Ti _0.985 Ni _0.015 )(O _2-st C _s N _t ), (Ti _0.98 Ni _0.02 )(O _2-st C _s N _t ), (Ti _0.97 Ni _0.03 )(O _2-st C _s N _t ) (Ti _0.99 Sr _0.01 )(O _2-st C _s N _t ), (Ti _0.97 Sr _0.03 )(O _2-st C _s N _t ), (Ti _0.95 Sr _0.05 )(O _2-st C _s N _t ), (Ti _0.97 Ba _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Ba _0.05 ) (O _2-st C _s N _t ), (Ti _0.94 Sn _0.05 Fe _0.01 ) (O _2-st C _s N _t ), (Ti _0.94 Sn _0.05 Ni _0.01 )(O _2-st C _s N _t ), (Ti _0.99 Fe _0.01 )(O _2-st C _s N _t ), (Ti _0.95 Zn _0.05 )(O _{2 -st} C _s N _t ), (Ti _0.77 Sn _0.15 Cu _0.08 ) (O _2-st C _s N _t ), (Ti _0.85 Zn _0.15 ) (O _2-st C _s N _t ), (Ti _0.90 Bi _0.10 ) (O _2-st C _s N _t ), (Ti _0.996 V _0.004 ) (O _2-st C _s N _t ), (Ti _0.984 V _0.016 ) (O _2-st C _s N _t ), (Ti _0.970 V _0.03 (O _2-st C _s N _t ), (Ti _0.997 MO _0.003 ) (O _2-st C _s N _t ), (Ti _0.984 MO _0.016 )(O _2-st C _s N _t ), (Ti _0.957 MO _0.043 )(O _2-st C _s N _t ), (Ti _0.97 W _0.03 )(O _2-st C _s N _t ), ( Ti _0.95 W _0.05 )(O _2-st C _s N _t ), (Ti _0.996 V _0.004 )(O _2-st C _s N _t ), (Ti _0.984 V _0.016 )(O _2-st C _s N _t ), Or (Ti _0.970 V _0.03 ) (O _2-st C _s N _t ).

Embodiment 26: The heterogeneous material of Embodiment 16, wherein the n-type semiconductor comprises (Ti _1-r M _r )(O _2-st C _s N _t ), wherein: M is tin; r is from 0 to 0.25 ;s is from 0.001 to 0.1; and t is from 0.001 to 0.1.

Embodiment 27. A heterogeneous material as in Example 26, wherein r is greater than zero.

Embodiment 28: The heterogeneous material of Embodiment 26, wherein r is 0, and the semiconductor comprises a rutile phase and an anatase phase.

Embodiment 29. The heterogeneous material of Embodiment 16, wherein the n-type semiconductor is tin oxide.

Embodiment 30: A method of decomposing a chemical composite comprising exposing a chemical compound to a photocatalyst in the presence of light, the photocatalyst comprising any of the homogeneous phase materials of Examples 1 to 29.

Embodiment 31: The method of Embodiment 30 wherein the chemical compound is a contaminant.

Embodiment 32: A method of killing a microorganism, the method comprising exposing the microorganism to a photocatalyst comprising the homogeneous phase material of any of Embodiments 1 to 29 in the presence of light.

Example 1: Synthesis Example 1 (a), Synthesis of n-type semiconductors (Ex-1)

Ti(CNO) ₂ :Sn(Ex-1): 3.78 g of tin(II) 2-ethylhexanoate (also known as tin(II)-isooctanoic acid (tin(II)) Octoate) and/or stannous octoate (Sp. Chemical, Inc., Gardiner, CA, USA) (Spectrum Chemicals, Gardena, CA, USA), 30 ml of 50 weight percent titanium (IV) double (Ammonium lactate) dihydrate (Titanium (IV) bis (ammonium lactato) dihydroxide) solution (lactic acid (titanium lactate) (Tyzor LA)) (Sigma Sigma Group, St. Louis, Missouri, USA) (Sigma Aldrich, St. Louis, MO, USA) and 15 grams of ammonium nitrate (NH ₄ NO ₃ ) (Sigma) The Qi Group, St. Louis, Missouri, USA) was dissolved in 25 ml of reverse osmosis (RO) purified water, then heated to 150 ° C and stirred for 20 minutes. The resulting mixture was then heated in a preheated muffle furnace at 350 degrees Celsius for 40 minutes under atmospheric conditions (room temperature) and atmospheric pressure. The resulting powder was placed in a preheated muffle furnace and then annealed at 475 degrees Celsius for 40 minutes under ambient conditions.

Example 1(b), load

The combusted synthetic Ti(O,C,N) ₂ :Sn (6 g) was mixed with 6 M HCl (60 ml) in a water bath at 90 ° C for 3 hours while stirring. The mixture was then cooled to room temperature, filtered through a 0.2 micron filter paper, washed with 100 to 150 milliliters of deionized water (DI), and finally dried overnight at room temperature for 10 to 15 hours.

The weight of copper used to treat Ti(O,C,N) ₂ :Sn (1 gram) is 0.01. 10 ml of an aqueous solution of CuCl ₂ .2H ₂ O (26.8 mg) and 1 gram of treated Ti (O) , C, N) ₂ : Sn was stirred at 90 ° C for 1 hour. Next, 1.5 ml of an aqueous solution containing NaOH (50 mg) and glucose (250 mg) was added to the reaction mixture at 90 ° C while stirring. After the addition of an aqueous solution of glucose and NaOH, the mixture was stirred for an additional hour, then cooled to room temperature, then filtered through a 0.2 micron filter, washed with 100 to 150 ml of deionized water and finally passed through an oven at 110 degrees Celsius. Dry (10 to 15 hours).

The weight ratio of CuO:Cu ₂ O of Ex-1 was determined to be 0.789:0.211. By comparison, the CuxO/TiO2 nanocomposite obtained according to the procedure described by Qiu et al., American Society of Chemistry, Nano-Journal, Vol. 6, No. 1609-1618, has a weight ratio of CuO:Cu ₂ O of 0.169: 0.831.

Example 1(b)', Comparative Example 0 (CE-0)

Copper and Sn-Ti(OCN) ₂ photocatalysts having a total weight of 0.25 wt.% CuO + 0.125 wt.% Cu ₂ O were physically mixed by hand using a mortar and pestle in 5 to 10 ml of methanol. This mixing action continues until the methanol has completely evaporated.

Example 1 (c), Comparative Example 1 (CE-1)

CE-1 (Ti(CNO) ₂ :Sn) was prepared in a similar manner to the procedure of Example 1 (a) except that the load CuxO was not performed (ie, only step A), and the result was completed without load Ti(CNO) ₂ : Sn (no Cu _x O).

Example 1 (d), Comparative Example 2 (Ex-1A)

Ex-1A was prepared in a similar manner to Example 1 (b) above, except that 25 mg instead of 50 mg NaOH and 125 mg instead of 250 mg glucose were used.

Example 1(d)', Comparative Example 2' (Ex-1B)

Ex-1B was prepared in a similar manner to the above Example 1 (b) except that the weight ratio of copper to the treated Ti(O, C, N) ₂ :Sn (1 g) was 0.005.

Example 1 (e), Comparative Example 3 (Ex-2 and Ex-3)

Ex-2 (plasma WO ₃ ) and Ex-3 (WO ₃ sold by Global Tungsten Powder Company (GTP)) were prepared in a similar manner to Ex-1 above, except that a plasma of WO ₃ or the mass was used. GTP-WO _{3 was} sold instead of Ti(O,C,N) ₂ :Sn photocatalyst; NaOH was not added to the reaction mixture and the amount of glucose was 125 mg instead of 250 mg. The plasmonics WO ₃ is manufactured in a similar preparation procedure as described in U.S. Patent Application Serial No. 13/738,243, filed on Jan. 10, 2013, which is incorporated herein by reference. . GTP-WO ₃ was obtained from Global Tungsten Powder Company (Twanda, Pennsylvania, USA) (Towanda, PA, USA) with no additional purification or annealing.

0.159 ml of a 1 molar solution of Bis(Ethylenediamine)copper(II)hydroxidate and 10 ml of reverse osmosis water and mix at 90 ° C and 1 g of WO ₃ hour. Next, glucose (125 mg) was added to the mixture while stirring at 90 °C. After the addition of the aqueous dextrose solution, the mixture was stirred for an additional hour, then cooled to room temperature, then filtered through a 0.2 micron filter, washed with 100 ml to 150 ml of deionized water and finally dried overnight in an air oven at 110 degrees Celsius. (10 hours to 15 hours).

Example 1 (f), Comparative Example 4 (Ex-4, Ex-5, Ex-6, CE-2)

Ex-4, Ex-5, Ex-6 and CE-2 were prepared in a similar manner to Ex-1 except that the same molar amount of CeO2 was used instead of Ti(O, C, N) ₂ :Sn. In addition, the loading conditions were modified as follows: Ex-4: aqueous solution of NaOH (25 mg) and glucose (125 mg); Ex-5: no glucose; Ex-6: glucose (62.5 mg) and NaOH (25 mg) Concentration.

CE-2 is similar to CE-1 except that CE-2 is the equivalent unloaded molar amount of CeO ₂ (than Ti(O, C, N) ₂ :Sn) (Sigma Sigma Group, St. Louis, Missouri, USA). CeO _{2 is used} from a state accepted by the supplier without additional purification or annealing.

Example 1 (g), Comparative Example 5 (Ex-7, CE-3)

Ex-7 was prepared in a similar procedure to Ex-1 above, except that the same molar amount of insulating agent Al ₂ O _{3 was used} instead of Ti(O,C,N) ₂ :Sn, using 25 mg of NaOH and using 125 mg of glucose. . The Cu _x O loading was 1% by weight relative to Al ₂ O ₃ . CE-3 is similar to CE-1 except that CE-3 is the equivalent unloading molar amount of Al ₂ O ₃ (than Ti(O, C, N) ₂ :Sn). Al ₂ O _{3 is used} from a state accepted by the supplier without additional purification or annealing.

Example 1 (h), Comparative Example 6 (Ex-8, CE-4)

Ex-8 was prepared in a similar manner to Ex-1 above, except that the same n-type UV-active photocatalyst was used instead of Ti(O, C, N) ₂ :Sn; 25 mg of NaOH and 125 mg of glucose were used. other than. The Cu _x O loading is 1 weight percent copper relative to Ta ₂ O ₅ . CE-4 is similar to CE-1 except that CE-4 is the equivalent unloading molar amount of Ta ₂ O ₅ (than Ti(O, C, N) ₂ :Sn) (Sigma Sigma Group, St. Louis, Missouri, USA). Ta ₂ O ₅ is used in a state acceptable from the supplier without additional purification or annealing.

Example 1 (i), Comparative Example 7 (Ex-9, Ex-10, Ex-11, Ex19, Ex-20, CE-4A)

Ex-9 was prepared in the same manner as Ex-1 described above except that an equivalent amount of n-type UV-active photocatalyst SnO _{2 was used} instead of Ti(O, C, N) ₂ :Sn. The Cu _x O loading is 1 weight percent copper relative to SnO ₂ . Nano-sized SnO ₂ (National Nanomaterials Research Institute, Houston, TX, USA) was annealed at 900 ° C for one hour at atmospheric pressure in a box furnace. It was then immersed in 6 M aqueous HCl as Ex-1. At Ex-10, the amount of NaOH was 25 mg and the amount of glucose used was 125 mg. In Ex-11, the amount of NaOH was 75 mg and the amount of glucose was 375 mg. In Ex-19 and Ex-20, the annealed SnO _{2 was} not soaked in 6 M aqueous HCl as described in Ex-1, Ex-10, Ex-11. In Ex-19, the amount of NaOH was 25 mg and the amount of glucose used was 3 mg. In Ex-20, the amount of NaOH is 25 mg and the amount of glucose is 10 mg. CE-4A is similar to CE-1 except that CE-4A is the equivalent unloading molar amount of SnO ₂ (than Ti(O, C, N) ₂ : Sn). There are different amounts of NaOH and glucose and a fixed amount of 1 weight percent copper relative to SnO ₂ is loaded, resulting in a different appearance color.

Example 1 (j), Comparative Example 8 (Ex-12, CE-5, Ex-13)

Ex-12 was prepared in the same manner as Ex-1B above. Loading Cu _x on rutile phase TiO ₂ (Japan Imperial Chemical Co., Ltd., Osaka, Japan) (Tayca, Inc. Osaka, JP), except using 25 mg instead of 50 mg NaOH and 125 mg instead of 250 mg Other than glucose.

CE-5 is similar to CE-1 except that CE-5 is the equivalent unloading molar amount of rutile phase TiO ₂ (Japan Imperial Chemical Co., Ltd., Osaka, Japan) (than Ti(O, C, N) ₂ : Sn). The rutile phase TiO ₂ is used in a state acceptable from the supplier without additional purification or exercise.

Ex- _13, 10 grams of commercially available WO ₃ (Global Tungsten Powder, Sylvania, PA, USA) was annealed at 400 degrees Celsius for one hour. [Pt(NH ₃ ) ₄ ]Cl ₂ (0.181 mg, Alfa Aesar, Ward Hill, MA, USA) (0.181 mg Alfa Aesar, Ward Hill, MA, USA) was dissolved in 15 ml of reverse osmosis water and It was stirred at room temperature (RT) for 2 hours together with 2 g of the annealed WO ₃ . Next, it was filtered through a 0.2 micron pore size filter membrane and washed with reverse osmosis water and dried overnight at 120 degrees Celsius. The resulting material was annealed for an additional hour at 400 degrees Celsius under the atmosphere.

Example 1 (k), Comparative Example 9 (Ex-13-17, CE-6)

Ex-14 to Ex-17 were prepared in the same manner as above except that different amounts of Pt(NH ₃ ) ₄ ]Cl ₂ and/or IrCl ₃ /IrO ₂ were dissolved in 15 ml of reverse osmosis water. See Table 1 for:

CE-6 is similar to CE-1 except that CE-5 is the equivalent unloading molar amount of WO ₃ (Global Tungsten Powder Company, Pennsylvania, USA) (than Ti(O, C, N) ₂ : Sn). WO _{3 is} used in a state acceptable to the supplier without additional purification or exercise.

Example 1 (l), Synthesis of n-type semiconductors (Ex-18)

Synthesis of MgTi2O5: 2.663 g of Mg(NO ₃ ) ₂ . 6H2O (Sigma Sigma Group, St. Louis, Missouri, USA), 5 grams of ammonium nitrate (Sigma Sigma Group, St. Louis, Missouri, USA), 1.5 grams of urea (Sigma Sigma Group, Saint Louis) , Missouri, USA) and 10 ml of Titanium (IV) bis (ammonium lactate) hydroxide (Tyzor LA) (Sigma Sigma Group, St. Louis, Missouri) , USA) Dissolve in 10 ml of deionized water in a 250 ml low heat resistant beaker. The resulting mixture was then heated to 350 degrees Celsius for 20 minutes in a preheated muffle furnace under atmospheric conditions (room temperature) and atmospheric conditions. The resulting powder was placed in a preheated muffle furnace and then annealed at room temperature of 600 degrees Celsius for 30 minutes.

MgTi ₂ O ₅ supported Cu _x O: Cu _x O was supported on MgTi ₂ O ₅ in a similar manner to the above Example 1 (b) except that during the preparation, no HCl preparation process was used. The procedure for the preparation of the NaOH used is similar to that described in Example 1 (b). The copper specific gravity of MgTi ₂ O ₅ was 0.01. 10 ml of an aqueous solution of CuCl ₂ ̇ 2H ₂ O (26.8 mg) was stirred with 1 g of MgTi ₂ O ₅ at 90 ° C for 1 hour. Next, a 1.5 ml aqueous solution containing NaOH (25 mg) and glucose (125 mg) was added to the reaction mixture at 90 ° C while stirring. After adding an aqueous solution of glucose and NaOH, the mixture was stirred for an additional hour and cooled to room temperature, then filtered through a 0.05 micron filter, washed with 100 to 150 ml of deionized water and dried in an oven at 110 degrees Celsius. About 2 hours.

Example 1 (m), (Ex-20 (Cu _x O loaded in complex phase TiO ₂ )

The complex phase of the n-type semiconductor was loaded on Cu _x O in a similar manner to Example 1 (b). The weight ratio of copper relative to the complex phase of n-type semiconductor (brand name P25 87% anatase phase TiO ₂ , 13% rutile phase TiO ₂ [Evonik Degussa, New Jersey, USA] [EvoniK Degussa, NJ, USA]) is 0.015 ml of CuCl ₂ . An aqueous solution of 2H2O (26.8 mg) was stirred with 1 g of P25 at 90 ° C for 1 hour. Next, a 1.5 ml aqueous solution containing NaOH (25 mg) and glucose (125 mg) was added to the reaction mixture at 90 ° C while stirring. After adding glucose and NaOH aqueous solution, the mixture was stirred for another hour and cooled to room temperature, subsequently filtered through a 0.05 micron filter, washed with 100 to 150 ml of deionized water, and at an air oven at 110 degrees Celsius. Dry for about 2 hours.

Example 1 (n), (CE-7)

Comparative Example CE-7 was prepared using a method similar to that of Example 1 (m) except that 0.25 wt.% CuO + 0.125 wt.% Cu ₂ O was physically mixed with 0.625 wt by hand in methanol (5-10 mL). % P25 until the methanol is completely evaporated at the end.

Example 1 (o), (Ex-19 AgVWO ₆ )

4.12 grams of vanadyl oxalate (American Strategic Mining Company, Arkansas, USA) (Stratcor, Inc, Arkansas, USA), 0.3 grams of glycine (Sigma Sigma Group, St. Louis, Missouri, US), 0.62 grams of ammonium nitrate (Sigma Sigma Group, St. Louis, Missouri, USA) and 1.484 grams of Ammonium meta tungstate (Global Tungsten Powder Company, Pennsylvania, USA) are dissolved together About 5 ml of reverse osmosis pure water. One gram of silver nitrate (Alfa Aesar, USA) was added to the solution to obtain a brown slurry in a 250 ml low-profile beaker, and then the resulting mixture was preheated under atmospheric conditions (room temperature) and atmospheric pressure. The muffle is heated to approximately 350 degrees Celsius for approximately 20 minutes. The resulting powder was then placed in a preheated muffle furnace and then annealed at 500 ° C for about 60 minutes under atmospheric conditions to give a yellow powder (Ex-19).

Example 1 (p), (Ex-20 (AgCa ₂ Zn ₂ V ₃ O ₁₂ ))

6.19 grams of vanadyl oxalate (US strategic mining company, Arkansas, USA), 1.11 grams of glycine (Sigma Sigma Group, St. Louis, Missouri, USA), 1.75 grams of zinc nitrate hexahydrate (zinc nitrate hexahydrate) Sigma Oric Group, St. Louis, Missouri, USA), 1.39 grams of Calcium nitrate tetrahydrate (Sigma Sigma Group, St. Louis, Missouri, USA), 2.49 grams of ammonium nitrate (Sigma) Qiqi Group, St. Louis, Missouri, USA) is dissolved together in about 10 ml of reverse osmosis (RO) pure water. 0.5105 Silver nitrate (Alfa Aesar, USA) was added to the solution to obtain a brown slurry in a 250 ml low-profile beaker, and then the resulting mixture was placed in a preheated muffle furnace at atmospheric (room temperature) and atmospheric pressure. Heat internally to approximately 350 degrees Celsius for 20 minutes. The resulting powder was placed in a preheated muffle furnace and annealed at 600 ° C for about 60 minutes under atmospheric conditions, resulting in a yellow powder (Ex-20).

Example 1 (q), (Ex-21 silver phosphate (Ag ₃ PO ₄ )

Five grams of silver nitrate (Alfa Aesar, USA) was dissolved in 10 ml of reverse osmosis (RO) pure water in a 50 ml low beaker. 1.128 grams of ammonium dihydrogen phosphate (Sigma Sigma Group, St. Louis, Missouri, USA) was dissolved in 10 ml of reverse osmosis (RO) pure water in a 50 ml glass beaker. The aqueous silver nitrate solution was titrated to the aqueous solution of ammonium dihydrogen phosphate while stirring the ammonium dihydrogen phosphate solution. The yellow precipitate formed at room temperature during this addition was finally filtered and dried in an air oven at 110 °C for 2 hours.

Example 2: Supporting Photocatalyst Characteristics Example 2(a), Characteristics of Powder X-Ray Diffraction (Ex-1A, CE-1, Ex-4, CE-2, Ex-7, and CE-3)

Sample powder samples of Ex-1A, CE-1, Ex-4, CE-2, Ex-7, and CE-3 utilize copper K-alpha radiation (Xigma Powder Diffractometer (Rigaku Miniflex II) [American Science, Inc., Woodland, Texas, USA]) (Rigaku Miniflex II [Rigaku Americas, Woodland, TX, USA) was analyzed by powder X-ray diffraction at 1 °/min. The results of X-ray diffraction analysis of Ex-1 and CE-1 are shown in Figure 3 and confirm the presence of anatase phase TiO ₂ . Also from the X-ray diffraction pattern (Fig. 3), it can be confirmed that the anatase phase of Ti(O, C, N) 2:Sn is maintained even after the Cu _x O load because of the result of the X-ray diffraction pattern. And the Joint Committee's Powder Compressed Standards (JCPDS) (New Town Plaza, Pennsylvania, USA) card no.00-021-1272[anatase-TiO ₂ ] JCPDS) shows the same peaks as basically the anatase phase map (the phase of the material is generally the activity of the visible light catalyst).

In addition, powder samples of the Examples Ex-4 and Ex-7 were analyzed in the same manner as Ex-1A above, except that the molar numbers of Ex-4 and Ex-7 were used instead of the Ex-1A. The results are shown in Figures 4 and 5, respectively, using powdered X-ray diffraction of copper K-alpha radiation (Xigma Powder Diffuser (Rigaku Miniflex II) [American Science, Inc., Woodland, Texas, USA]) ° / minute. The X-ray diffraction results are shown in Figures 4 and 5 and it is determined that the Cu _x O loading does not substantially affect the bulk semiconductor phase of each n-type material.

Example 2(b): Diffuse Reflectance Spectroscopy (DRS) Characteristics

Powder samples of Ex-1A, CE-1 (Fig. 6); Ex-4 and CE-2 (Fig. 7), Ex-7 and CE-3 (Fig. 8) together using diffuse reflectance spectroscopy (DRS) analysis . The results are shown in Figures 6, 7, and 8, and show that at least tin-doped (Ex-1A), CeO ₂ (Ex-4), and Al ₂ O ₃ (Ex-7) exhibit increased visible spectrum. (400 nm - 800 nm) absorption, and CE-1, CE-2 and CE-3 are not. Therefore, anatase phase TiO ₂ was observed in the X-ray diffraction spectrum and the visible light absorption spectrum because Ti(O, C, N) ₂ : Sn, CeO ₂ , and Al ₂ O _{3 were} determined due to the anatase phase. Loaded on the substrate. The supported Cu _x O has an absorption spectrum on the longer wavelength side of the absorption edge of the semiconductor, and if the supported Cu _x O has a mixture of CuO and Cu ₂ O, the absorption characteristics thereof are observed to be 600 nm and respectively. Between 800 nm and between 500 nm and 600 nm, in addition to the absorption of Cu _x O under load.

Example 3. Establishment of Photocatalytic Experiments (Ex-1A and CE-1)

Ex-1A (130 mg) was made as described in the above method of the present disclosure, and 1.04 ml of deionized water was added to make a coating solution of 10% by weight of solid material in water. As a result, the dispersant was homogenized using an ultrasonic homogenizer. The glass substrate (50 mm x 75 mm) was coated with the product prepared above using a spin coater (1200 rpm / 40 sec). The coated substrate was heated at 120 degrees Celsius for two minutes. The other was prepared in the same manner except that Ex-1A was replaced by the example CE-1 (130 mg).

The glass piece after spin coating was heated at 120 degrees Celsius for 1 hour under full spectrum irradiation on a hot plate by a xenon lamp (lamp output power of 300 watts). Each piece was then sealed under vacuum with a respective 5 liter air sampling bag (Tedlar bag), followed by injection of 3 liters of atmosphere and 80 ml of 3500 ppm of acetaldehyde. Each bag was gently pressed by hand for 2 minutes and then placed in the dark for 15 minutes. The acetaldehyde concentration was estimated to be 80 ± 2 ppm by a gas chromatography-flame ionization detector (GC-FID). Each air sampling bag containing the sample was placed in the dark for 1 hour. The face/air sampling bag was exposed to a 455 nm blue light emitting diode having a light intensity of 270 mW/cm 2 . The same was collected every 30 minutes by an auto-injection well of a gas chromatography-flame ionization detector, and the remaining amount of acetaldehyde was estimated over the next 30 minute interval. Fig. 9 is a diagram showing the VOC performance data of the exemplary Ex-1A. The figure shows that when Ti(CNO) ₂ :Sn and Cu _x O (example Ex-1A) are combined, the performance is better than Ti(CNO) ₂ :Sn(CE-1) alone.

Example 4, antibacterial experiment Example 4A

The substrate (1 inch X 2 inch glass slide) was continuously applied with 70% isopropanol (IPA) and 100% ethanol (EtOH) to prepare and then dried in air. example Ex-1B was dispersed in 100% ethanol at 2 mg/ml, and then 100 μl of the suspension was added to the substrate and dried. The application process was repeated five times until 1 mg of the sample Ex-1B was reached on the substrate. The substrate was dried at room temperature. The coated substrate was placed in a glass dish containing water-wet filter paper to keep it wet, and the glass was interposed between the substrate and the filter paper to separate the glass sheets.

Escherichia coli (ATCC 8739) was streaked in a 10 cm diameter petri dish containing 20 ml of LB (lysogeny broth/luria broth) and cultured overnight at 37 degrees Celsius. In each experiment, each single colony was picked and inoculated into 3 ml of nutrient base, and the inoculated culture was cultured at 37 degrees Celsius for 16 hours to create an overnight culture (about 109 cells/ml). By diluting the overnight culture 100-fold, the fresh log phase culture of the overnight culture was obtained and cultured in a petri dish containing another 5 cm diameter in LB containing vegetables and incubated at 37 degrees Celsius for 2.5 hours. The fresh culture was then diluted 50-fold with 0.85% saline, which was administered a cell suspension of 2 x ¹⁰⁶ cells/ml. 50 microliters of the cell suspension was pipetted onto each of the deposited glass substrates. A sterilized (at 70% followed by 100 EtOH) plastic filter (20 mm x 40 mm) was placed over the suspension to spread evenly under the filter. The sample was stored in the dark (Cu _x O ₂ - dark) or under blue light-emitting diode light (wavelength 455 nm, 10 mW/cm 2 ) (CuO ₂ - light). At selected time points, such as 30 minute/60 minute increments, the sample was placed in 10 milliliters of 0.85% saline and vortexed to wash off the bacteria. The washing of the suspension was continued, followed by serial dilution with 0.85% saline, and then placed in LB amaranth and cultured overnight at 37 degrees Celsius to determine the number of living cells, the so-called colony forming units/samples.

The results are shown in Figures 10 and 11. The characteristic of killing E. coli was apparently due to the presence of flexible copper ions even in the darkness of 30 minutes (see Figures 10 and 11).

Figure 10 also shows the performance of completely killing E. coli in the dark and in the blue light-emitting diode of 455 nm at 10 mW/cm ₂ after Cu+ loading on CeO ₂ . Therefore, Cu _x O loading on CeO ₂ is a good function for removing Escherichia coli.

Example 4B

Example Ex-1 powder was prepared as described in Example 1. The powder was then held in the dark at a relative humidity of 85% and 85 degrees Celsius for 7 days. The slides were then prepared and tested for antibacterial activity in the same manner as described in Example 4A. The results are shown in Figure 12A. The results show that the Ex-1 exhibits photocatalytic activity even after exposure to 85% relative humidity and 85 degrees Celsius for 7 days.

Example 4C

Example Ex-7 powder was prepared as described above. The powder was stored in the dark at 300 degrees Celsius for 20 minutes. The slides were then prepared and tested for antibacterial activity in the same manner as in Example 4A above. The result is shown in Figure 12B. The results show that Ex-7 maintains its photocatalytic activity even after exposure to 300 degrees Celsius for 20 minutes.

Example 5: Photocatalyst experiment of dye discoloration study Example 5A

The photocatalytic properties of Ex-1, CE-1 and the rutile phase of TiO ₂ loaded or unloaded in the Cu _x O system are measured by food additive dyes (natural blue powder, ColorMaker, Anaheim, CA). , US) degradation compared to a natural blue powder 2.85 grams dissolved in 100 ml of reverse osmosis water to create a blue powder stock solution. 150 mg of each sample was placed in reverse osmosis water (27 ml) and mixed with 3 ml of natural blue in a blue powder stock solution for 1 hour without any light and exposed to blue light-emitting diodes (455 Nai) Meter, 45mW / square centimeter) 5 hours. By using ultraviolet-visible absorption spectroscopy at 1 hour, 3 hours, and 5 hours (Cary-50, spectrophotometer, Agilent Technologies, Santa Clara, Calif., USA) (Cary-50, Spectrophotometer Agilent Technologies, Santa Clara, CA) , USA) monitor its concentration to measure the degradation of the blue solution. The concentration was calculated when the light wave intensity was 600 nm. The result is shown in Figure 13. Table 2 below compares the final degradation results of the four photocatalytic materials.

5B

The photocatalytic performance of the sample Ex-18 (Cu _x O supported on MgTi ₂ O ₅ ) is measured by measuring the dye additive like natural blue powder (natural blue powder, ColorMaker, Anaheim, California, USA) Degradation to detect). Degradation was detected as in the manner of Example 5A above. The results are shown in Figure 17.

Photocatalyst experiment for antibacterial research example 6A

Each of the 130 mg powder samples (Ex-14 to Ex-18 described above) was simultaneously dissolved in a minimum of reverse osmosis pure water (ca-15 ml) and homogenized for 5 minutes.

The clean culture dish is rinsed with ethanol and the internal surface is plasma-coated Ionize for 1 to 2 minutes. A homogenized sample of each compound was poured into the treated petri dish and heated at 120 degrees Celsius while agitating to increase the homogenous distribution of the sample as it dried. After the sample was dried, the dish was placed under an ultraviolet lamp (300 watts) for 1 hour. Each dish was then sealed under vacuum with a 5 liter air sampling bag, followed by 3 liters of ambient air and 80 ml of 3500 ppm acetaldehyde. Each bag was gently pressed by hand for 2 minutes and then placed in the dark for 15 minutes. The concentration of acetaldehyde was estimated to be 80 ± 2 ppm by a gas chromatography-flame ionization detector (GC-FID). Each air sampling bag containing the sample was placed in the dark for 1 hour. The slide/air sampling bag was exposed to a 455 nm blue light emitting diode array having a light intensity of 0.656 mW/cm 2 . A sample was collected every 30 minutes by an auto-injection well of a gas chromatography-flame ionization detector and the amount of acetaldehyde remaining was detected at intervals of the next 30 minutes. The results are shown in Table 3 below.

Figure 14 shows WO3 (commercial GTP) (CE-6), 0.05 mol% platinum loaded WO3 (Ex-13), 0.1 mol% IrO ₂ loaded WO ₃ (Ex-16) and 0.05 mol% at the same time The decomposition rate (Ct/Co) of acetaldehyde of platinum and 0.1 mol% IrO ₂ supported WO ₃ (twice) (Ex-17). Interestingly, the observations have a positive effect on the platinum loading and the acetaldehyde decomposition of the IrO ₂ alone loaded WO3 at 455 nm (light intensity 0.656 mW/cm 2 ) of blue light-emitting diodes has no effect. However, when both platinum (0.05 molar percentage) and IrO ₂ (0.1 mole percentage) were loaded on WO ₃ , compared to platinum alone (0.05 mol%) or IrO ₂ alone (0.1 mol%) or just alone The same conditions of GTP WO3 can lead to further enhancement of the photodegradation ability of acetaldehyde.

Example 5c

Ex-10 photocatalytic properties (SnO ₂ ), CE-4A and individual food additive dye FD&C Blue No. 2 dye by measuring food additive dye FD&C Blue No. 2 dye (synthetic blue powder, wide code The degradation of the technology company, Michigan, USA) (Synthetic blue colored powder, Chromatech, Inc, Michigan, USA) was compared. Gram's natural blue powder is soluble in 100 ml of reverse osmosis water to create a blue powder stock solution. Place 150 mg per sample. The photocatalyst characteristics were determined in the same manner as in Example 5a. The result is shown in Figure 15.

Comparison of Ex-18 (MgTiO ₅ ) and Ex-1 (SnTi (OCN) by measuring the degradation of food additive dye FD&C Blue No. 2 dye (synthetic blue powder, K.K., Michigan, USA) _2: ) Photocatalyst characteristics of the load (CuxO). 2.85 grams of natural blue powder was dissolved in 100 milliliters of reverse osmosis water and a blue powder stock solution was prepared. Place 150 mg per sample. The photocatalytic properties were determined in the same manner as described in Example 5a. The results are shown in Figure 16.

Example 6. Photocatalytic Deactivation of E. coli (ATCC 8739) Example 6A method:

The substrate (1 inch X 2 inch slide) was prepared by sequential application with 70% isopropanol and 100% ethanol followed by drying in air. Example Ex-1B was applied to a substrate at a concentration of 100% ethanol in a concentration of 2 mg/ml and then about 100 microliters, followed by drying. This application procedure was repeated 5 times to obtain about 1 mg of the sample Ex-1B on the substrate. The substrate was then dried at room temperature. The coated substrate was placed in a glass petri dish impregnated with filter paper to keep it moist. A glass spacer is interposed between the substrate and the filter paper to separate the substrate from the filter paper.

Escherichia coli (ATCC 8739) was streaked in a petri dish containing 5 ml of LB acacia in a diameter of 5 cm and cultured overnight at 37 degrees Celsius. In each experiment, a single colony was selected and inoculated into about 3 ml of nutrient base, and inoculated on a medium at about 37 degrees Celsius for about 16 hours to produce an overnight medium (about ¹⁰⁹ cells/ml). By diluting the overnight culture 100-fold, the fresh log phase culture of the overnight culture can be obtained and inoculated into an additional 5 cm diameter petri dish containing LB agar and cultured at 37 degrees Celsius for 2.5 hours. The fresh culture was then diluted 50-fold and a cell suspension of approximately 2 x ¹⁰⁶ cells/ml was administered. 50 microliters of the cell suspension was suspected to each glass substrate. A sterilized (70% followed by 100 ethanol) plastic filter (20 mm x 40 mm) was placed on the suspension to spread evenly under the filter. At the selected time point, such as in about 30 minute increments, the sample was placed in 10 ml of 0.85% saline and centrifuged at 3200 rpm for about 1 minute to wash off the bacteria. The suspension was washed sequentially with 0.85% saline, then placed in LB amaranth and cultured overnight at 37 degrees Celsius to determine the number of living cells, the so-called colony forming units/samples. Counting is done by visual inspection and multiplying the result by the dilution factor to reach the determined amount. The sample was then irradiated with a blue light emitting diode providing about 455 nm of about 45 mW/cm ₂ and placed in a blue light emitting diode of 455 nm at 45 mW/cm ₂ . The result is shown in Figure 19.

The antibacterial properties of the Examples CE-7 and Ex-7A were determined in the same manner as described in Example 6A, except that CE-7 and Ex-7A were used in the same molar amount instead of Ex-1B. The results are shown in Figure 17 (CE-7) and Figure 18 (Ex-7A).

Example Ex-1 (loaded at 1% Cu _x O/Sn:Ti(OCN) ₂ : tin), only Cu _x O and unloaded Sn:Ti(OCN) ₂ (as described in Example 1(a)) Antibacterial properties were compared by calculating the antibacterial activity as described in Example 6A. The result is shown in Figure 20.

Photocatalyst function I

50 mg of Cu _x O/P25 (as produced by Example 1 (m)) and 1 ml of 10% bleach (Colox Germincidal, NaClO based) in 1.6 ml Mix in a microcentrifuge tube and incubate for two hours at room temperature (approximately 24 degrees Celsius) (VWR vortex mixer set to 9). After the incubation, the tubes were centrifuged in a microcentrifuge tube 5430 microcentrifuge (2 minutes 14167 relative centrifugal force), after which particulate matter formed to form a solid precipitate at the bottom of the centrifuge tube. The clean supernatant should be carefully removed and 1 ml of deionized water added. The sediment that completely oscillated the centrifuge tube to the bottom was completely broken up and evenly distributed and the suspension became homogeneous. Centrifuge again. The above steps should be repeated four more times.

After the last centrifugation, the solid precipitate was resuspended in 1 ml of deionized water and mixed with 4 ml of deionized water in a 20 ml clean covered glass vial, and 5 ml of methanol was added to make the total volume in the bottle About 10 ml.

A magnetic stir bar (1/2 inch x 1/8 inch, disposable) was added to the bottle and placed on a stirrer (1000 rpm). The 300 watt xenon lamp (Oriel 68811) was placed 15 cm from the bottle. The radiation exposure lasted for 1 hour in the fume hood, and the temperature change within the bottle was negligible during this process.

After irradiation, the contents of the bottle are centrifuged to remove all liquid. Precipitate Dry in vacuo and resuspend in 25 ml of 200 pure ethanol. The mixture was then shaken for 20 minutes with an ultrasonic oscillator.

Spread 100 μl of the oscillating dispersion onto a 1 inch X 2 inch piece of glass. After the surface is dry (in a fume hood), the process is repeated and a total of five layers are applied. The coated slides were used for the bacterial test of this standard.

For the purpose of the control group, 50 mg of Cu _x O/Al ₂ O _{3 was} treated in the same manner as above, and then used to fabricate coated slides. This control slide was used for standard bacterial testing in the same manner as Cu _x O/P25. The results from the dark test are plotted as a graph.

As shown in Figure 22, (left), the newly generated Cu _x O/P25(1) exhibited high activity and reduced E. coli 3 log units in 30 minutes in the dark. The bleached material (2) exhibited a greatly reduced activity, which was reduced by 3 log units only after 2 hours in the dark. Once bleached, the material was irradiated with a xenon lamp, however, as a result, the activity exhibited by sample (3) compared to the untreated sample (1) also reached a three log reduction after 30 minutes.

In contrast, this recovery by radiation is not seen in the case of copper oxide/Al ₂ O ₃ (Fig. 22, right), as shown by bleached or irradiated samples (3). The activity was similar to that of the bleach-treated sample (2), but was significantly lower than the fresh sample (1).

Photocatalyst function II

In order to investigate how the time of the bleaching treatment affects the activity of the material supporting the copper oxide, the above experiment was carried out and set for 2 and 16 hours with the bleaching treatment time. All other experimental aspects remain the same. The results of the log reduction of these treated samples are plotted along with the untreated material.

In Figure 23, on the left, bleached treated Cu _x O/Al ₂ O ₃ resulted in a significant drop in dark activity. Testing under light does not rebuild any significant activity. In contrast, in the case of Cu _x O/photocatalyst (P25) (Fig. 23, right panel), although the dark activity was similarly affected, the high light activity was reconstructed. The focus of this experiment is that even after 16 hours of bleaching, the photoreactivity reproducibility process is still quite intact, which strongly demonstrates the durability of Cu _x O/P25.

Aqueous catalytic synthesis of doped WO3 boron: The method of water combustion synthesis is used to prepare WO ₃ doped boron in a small stage (Epsilon phase).

5 grams of Ammonium Meta Tungstate hydrate (Inverman Advanced Materials, Manchester, Connecticut, USA) (Inframat Advanced Materials, Manchester, CT, USA), 100 mg of boric acid (Sigma) Oric Group, St. Louis, Missouri, USA), 2 grams of Carbohydrazide (Sigma Sigma Group) and 10 grams of ammonium nitrate (Sigma Sigma Group) dissolved in 50 ml of deionized water in. The aqueous solution is then placed in a muffle furnace and preheated to about 420 degrees Celsius until the end of the combustion is complete (about 20 minutes). After the end of combustion, the product was annealed at 425 ° C for about 30 minutes under air. The powder body appearance color appears orange and is diffracted by X-ray diffraction of powder X-ray diffraction pattern (Fig. 1) and standard small amount (epsilon) WO ₃ (ICFF PDF card number 01-087-2404) Compare to confirm.

Figure 1: Powder X-ray diffraction pattern (right)

Surface modification of a small amount of WO ₃ by cobalt and selective adsorption method using cobalt oxide

One gram (gm) of small amount of WO ₃ and 40.37 grams of CoCl ₂ ̇ 4H ₂ O were dissolved in about 10 ml of deionized water and stirred at 90 ° C for about 2 hours in a 40 ml closed reactor. Next, the closed reactor was cooled with tap water and filtered through a filter membrane (fine 0.05 micropores), washed several times with deionized water (at least about 250 ml) and finally dried at 110 ° C for two hours to obtain a small cobalt oxide load. Amount of WO ₃ .

Unless otherwise indicated, all numbers expressing the quality and characteristics of the ingredients, such as molecular weight, reaction conditions, and all those described in the specification and patent application are to be construed as being modified by the word "about" in all instances. Accordingly, unless stated to the contrary, the numerical parameters set forth in the specification and the appended claims are the approximations that may vary depending on the desired properties sought. At the very least, and without attempting to limit the application of the teachings equivalent to the equivalents of the claims, each numerical parameter should be construed in accordance with the number of significant digits reported and by applying the ordinary rounding technique.

The terms "a", "an", "the" and "the" are used in the description of the invention, particularly in the context of the following claims. Unless otherwise stated herein or the context clearly contradicts. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted. The use of any and all examples herein, or exemplary language, such as "such as", No language in the specification should be construed as indicating that any element not claimed is essential to the practice of the invention.

The other element groups of the embodiments disclosed herein are not to be construed as limiting. Each group element can be considered as a separate claim or arbitrarily combined with other elements of the group or other elements herein. It is expected that for convenience and / or patentability For sexual reasons, one or more elements of a group may be included or deleted from a group. When any such inclusion or deletion occurs, the specification is considered to include a group as a modification to achieve a written description of all of the Markusi groups used in the appended claims.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, differences from the described embodiments will become apparent to those of ordinary skill in the art. The inventors expect that those skilled in the art will employ these differences as appropriate, and the inventors intend that the invention may be practiced otherwise than as specifically described herein. Accordingly, the scope of the patent application contains all modifications and equivalents to the scope of the patent application, which is subject to the applicable law. In addition, any combination of the above-described elements in all possible forms of the differences is intended to be inconsistent with the context unless otherwise indicated herein.

It should be understood that the embodiments disclosed herein are illustrative of the principles of the claimed invention. Other modifications that may be used are within the scope of the patent application. Accordingly, other embodiments may be utilized in accordance with the teachings herein. Therefore, the scope of patent application is not limited to the embodiments shown and described.

Claims (32)

A heterogeneous material comprising: a p-type semiconductor comprising a first metal oxidizing compound and a second metal oxidizing compound, wherein the first metal oxidizing compound and the second metal oxidizing compound have different oxidation states of the same metal And wherein the p-type semiconductor has a p-type valence band; and an n-type semiconductor having an n-type valence band deeper than the p-type valence band, wherein the n-type semiconductor is in ionic charge communication with the p-type semiconductor. The heterogeneous material according to claim 1, further comprising a noble metal in ionic charge communication with the first metal oxidizing compound and the second metal oxidizing compound. The heterogeneous material according to claim 2, wherein the noble metal is ruthenium, rhodium, palladium, silver, rhodium, platinum or gold. The heterogeneous material of claim 2, wherein the noble metal is supported on the n-type semiconductor. The heterogeneous material of claim 1, further comprising a second n-type semiconductor, wherein at least a portion of the second n-type semiconductor is ionically isolated from the p-type semiconductor. The heterogeneous material of claim 5, wherein the second n-type semiconductor comprises a tantalum oxide. The heterogeneous material according to claim 6, wherein the cerium oxide is CeO ₂ . The heterogeneous material of claim 5, wherein the second n-type semiconductor comprises a complex phase TiO ₂ . The heterogeneous material according to claim 1, wherein the first metal oxide compound comprises monovalent copper and the second metal oxide compound comprises divalent copper; the first metal oxide compound comprises divalent cobalt The second metal oxidizing compound comprises trivalent cobalt; the first metal oxidizing compound comprises divalent manganese and the second metal oxidizing compound comprises trivalent manganese; the first metal oxidizing compound comprises ferrous iron and the second metal oxidizing compound comprises Ferric iron; or the first metal oxidizing compound comprises trivalent cerium and the second metal oxidizing compound comprises tetravalent cerium. The heterogeneous material of claim 1, wherein the p-type semiconductor is loaded onto the n-type semiconductor. The heterogeneous material of claim 1, wherein the p-type semiconductor is substantially uniformly dispersed over the n-type semiconductor. The heterogeneous material according to claim 1, wherein the p-type semiconductor is in the form of particles having a particle diameter of 100 nm or less. The heterogeneous material according to claim 9, wherein the p-type semiconductor comprises monovalent copper and divalent copper. The heterogeneous material of claim 13, wherein the p-type semiconductor comprises copper oxide. The heterogeneous material of claim 14, wherein the copper oxide is chemically valence controlled. The heterogeneous material according to claim 9, wherein the ratio of monovalent copper to divalent copper is between 10:90 and 30:70. The heterogeneous material of claim 1, wherein the p-type semiconductor is from 0.001 to 10 weight percent of the heterogeneous material, and the n-type semiconductor is from 90 to 99.999 weight percent of the heterogeneous material. The heterogeneous material according to claim 1, wherein the n-type semiconductor is an oxide of tantalum, tungsten, lanthanum, tin, zinc, lanthanum, zirconium, hafnium, indium, or aluminum. The heterogeneous material according to claim 1, wherein the n-type semiconductor comprises Sn-Ti(O, C, N) ₂ ), MgTi ₂ O ₅ , CeO ₂ , KTaO ₃ , Ta ₂ O ₅ , SnO ₂ , WO ₃ , ZnO, SrTiO ₃ , BaTiO ₃ , ZrTiO ₄ , In ₂ TiO ₅ , Al ₂ TiO ₅ or LiCa ₂ Zn ₂ V ₃ O ₁₂ . The heterogeneous material according to claim 1, wherein the n-type semiconductor is Al _2-x In _x TiO ₅ , wherein 0 < x < 2. The heterogeneous material according to claim 1, wherein the n-type semiconductor is Zr _1-y Ce _y TiO ₄ , wherein 0 < y < 1. The heterogeneous material according to claim 1, wherein the n-type semiconductor is a titanium oxide having a monovalent band controlled by doping. The heterogeneous material according to claim 1, wherein the n-type semiconductor is titanium oxide doped with nitrogen, carbon or both. The heterogeneous material according to claim 1, wherein the n-type semiconductor is titanium oxide comprising a compound represented by the chemical formula (Ti _1-r M _r )(O _2-st C _s N _t ), wherein :M is tin, nickel, ruthenium, osmium, iron, ruthenium, vanadium, molybdenum, tungsten, zinc, copper or a combination thereof; r is from 0 to 0.25; s is from 0.001 to 0.1; and t is from 0.001 to 0.1. The heterogeneous material according to claim 24, which comprises (Ti _0.99 Sn _0.01 ) (O _2-st C _s N _t ), (Ti _0.97 Sn _0.03 ) (O _2-st C _s N _t ) (Ti _0.95 Sn _0.05 )(O _2-st C _s N _t ), (Ti _0.90 Sn _0.10 )(O _2-st C _s N _t ), (Ti _0.85 Sn _0.15 )(O _2-st C _s N _t ), (Ti _0.985 Ni _0.015 ) (O _2-st C _s N _t ), (Ti _0.98 Ni _0.02 ) (O _2-st C _s N _t ), (Ti _0.97 Ni _0.03 ) (O _2-st C _s N _t ), (Ti _0.99 Sr _0.01 )(O _2-st C _s N _t ), (Ti _0.97 Sr _0.03 )(O _2-st C _s N _t ), (Ti _0.95 Sr _0.05 )(O _2-st C _s N _t ), (Ti _0.97 Ba _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 Ba _0.05 ) (O _2-st C _s N _t ), (Ti _0.94 Sn _0.05 Fe _0.01 ) (O _{2- St} C _s N _t ), (Ti _0.94 Sn _0.05 Ni _0.01 ) (O _2-st C _s N _t ), (Ti _0.99 Fe _0.01 ) (O _2-st C _s N _t ), (Ti _0.95 Zn _0.05 ) O _2-st C _s N _t ), (Ti _0.77 Sn _0.15 Cu _0.08 ) (O _2-st C _s N _t ), (Ti _0.85 Zn _0.15 ) (O _2-st C _s N _t ), (Ti _0.90 Bi _0.10 )(O _2-st C _s N _t ), (Ti _0.996 V _0.004 )(O _2-st C _s N _t ), (Ti _0.984 V _0.016 )(O _2-st C _s N _t ), (Ti _0.970 V _0.03 )(O _2-st C _s N _t ), (Ti _0.997 Mo _0.003 )(O _2-st C _s N _t ), (Ti _0.984 Mo _0.016 ) (O _2-st C _s N _t ), (Ti _0.957 Mo _0.043 ) (O _2-st C _s N _t ), (Ti _0.97 W _0.03 ) (O _2-st C _s N _t ), (Ti _0.95 W _0.05 ) (O _2-st C _s N _t ), (Ti _0.996 V _0.004 ) (O _2-st C _s N _t ), (Ti _0.984 V _0.016 ) (O _2-st C _s N _t ), or (Ti _0.970 V _0.03 ) (O _2-st C _s N _t ). The heterogeneous material according to claim 16, wherein the n-type semiconductor comprises (Ti _1-r M _r )(O _2-st C _s N _t ), wherein: M is tin; r is from 0 To 0.25; s is from 0.001 to 0.1; and t is from 0.001 to 0.1. A heterogeneous material as described in claim 26, wherein r is greater than zero. The heterogeneous material of claim 26, wherein r is 0, and the semiconductor comprises a rutile phase and an anatase phase. The heterogeneous material according to claim 16, wherein the n-type semiconductor is a tin oxide. A method of decomposing a chemical compound, comprising exposing the chemical compound to a photocatalyst in the presence of light, the photocatalyst comprising a homogeneous material as described in claim 1 of the patent application. The method of claim 30, wherein the chemical compound is a contaminant. A method of killing a microorganism comprising exposing the microorganism to a photocatalyst comprising a homogeneous material as described in claim 1 of the patent application in the presence of light.