JP2016512164A - Multivalent photocatalytic heterogeneous materials for semiconductors - Google Patents

Abstract

The present specification includes a p-type semiconductor including two metal oxide compounds of the same metal in two different oxidation states, an n-type semiconductor having a valence band deeper than that of the p-type semiconductor, And heterogeneous materials in which these semiconductor types are in ion communication with each other. Heterogeneous materials enhance photocatalytic activity. [Selection] Figure 1

Description

Inventors: Ekambaram Sambandan and Bin Zhang
The present disclosure is a heterogeneous material having a p-type semiconductor including a mixed-valence oxide compound and an n-type semiconductor having a valence band deeper than that of the p-type semiconductor, A heterogeneous material in communication with a mixed-valence oxide compound of type semiconductor by ionic charge is described. These polyvalent heterogeneous materials can be used to enhance the photocatalytic activity of the photocatalytic material.

Visible light activated photocatalysts can be deployed for self-cleaning, air and water purification, and many other interesting applications, usually without post-deployment non-renewable energy costs. This photocatalyst is because it decompose contaminants using ambient light, such as solar radiation or indoor and outdoor lighting (dye, volatile organic compounds, and NO _x, etc.). With the anticipated rapid adoption of UV-free indoor lighting (such as LEDs and OLEDs), indoor applications such as indoors in limited areas such as homes, public and commercial spaces, especially aircraft and public buildings There is an urgent need to find a way to arrange a visible light activated photocatalyst for air purification. In addition, additional applications for antimicrobial surfaces and self-cleaning materials have broad applicability in the areas of food service, transportation, health care, and hospitality.

Elemental copper, copper composites, alone or in combination with metal oxides, have been described as useful photocatalytic / antimicrobial / antiviral materials. US Patent Publication Nos. 2007/0154561, 2009/0269269, 2011/0082026, and 2012/02201714; and Qiu, Xiaoqing et al., “Hybrid Cu _x O / TiO ₂ as a risk reducing material in indoor environments. See Nanocomposites (Hybrid Cu _x O / TiO ₂ Nanocomposites as risk-reduction materials in indoor environments), ACS Nano, 6 (2): 1609-1618 (2012). However, elemental copper exhibits a decrease in antibacterial activity over time (durability) and an unattractive aesthetic change (from Cu metal to black CuO), both in the oxidation of elemental copper under normal application conditions It is thought to be caused. Therefore, there is a need for an improved lifetime of antimicrobial activity over time. Therefore, there is a need for a photocatalytic material that provides antibacterial / antiviral activity without any unattractive aesthetic change.

  The present disclosure is a heterogeneous material having a p-type semiconductor comprising a mixed valence oxide compound and an n-type semiconductor having a valence band deeper than that of a p-type semiconductor, wherein the semiconductors are Describes a heterogeneous material in communication by ionic charge. These polyvalent heterogeneous materials can be used to increase the photocatalytic activity of the photocatalytic material and to improve durability (ie, maintain photocatalytic activity over time). The photocatalytic material is useful for having and / or enhancing antibacterial (light / dark) activity, antiviral activity, degradation of volatile organic compounds (VOC), and / or dye discoloration in aqueous solution.

  Some embodiments are: a p-type semiconductor comprising a first metal oxide compound and a second metal oxide compound, wherein the first metal oxide compound and the second metal oxide compound are of the same metal A p-type semiconductor having different oxidation states and having a p-type valence band; and an n-type semiconductor having an n-type valence band deeper than the p-type valence band, the ionic charge with respect to the p-type semiconductor A heterogeneous material including an n-type semiconductor in communication therewith.

  Another embodiment further comprises a noble metal in communication with the mixed valence oxide compound by ionic charge. In another embodiment, the noble metal is rhodium, ruthenium, palladium, silver, osmium, platinum, or gold. In another embodiment, the noble metal is injected into the n-type semiconductor.

Another embodiment further includes a second n-type semiconductor in which at least a portion of the second n-type semiconductor is an ionic charge isolated from the mixed valence oxide compound. In another embodiment, the second n-type semiconductor includes cerium oxide. In another embodiment, the cerium oxide is CeO _2. In another embodiment, the second n-type semiconductor comprises multi-phase TiO ₂ .

  In another embodiment, the mixed valence oxide compound comprises a pair of identical metal chemical elements, such as Cu, Co, Mn, Fe, Ir, etc., in two different oxidation states, such as copper (I) and copper (II A pair of cobalt (II) and cobalt (III); a pair of Mn (II) and Mn (III); a pair of Fe (II) and Fe (III); or Ir (III) Included in pairs with Ir (IV).

  In another embodiment, the p-type semiconductor is injected into the n-type semiconductor.

  In another embodiment, the p-type semiconductor is substantially uniformly distributed on the n-type semiconductor. In another embodiment, the mixed valence oxide compound has a particle size of 100 nm or less.

In another embodiment, the copper (I) and copper (II) compounds are Cu _x O compounds. In another embodiment, the Cu _x O compound is chemically controlled in valence. In another embodiment, the ratio of copper (I): copper (II) is between 10:90 and 90:10.

  In another embodiment, the p-type semiconductor is 0.001 to 10% by weight of the heterogeneous material and the p-type semiconductor is 90 to 99.999% by weight of the heterogeneous material.

The n-type semiconductor can be any suitable semiconductor in which the charge carrier is an electron, such as an electron in a conduction band donated from the donor band of the dopant. In another embodiment, the n-type semiconductor is an oxide, including oxides of cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, or aluminum. 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, n-type semiconductor is _{Al 2-x In x TiO 5} ( wherein a 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 include an oxide including titanium. In another embodiment, the oxide comprising titanium comprises multi-phase titanium oxide. In another embodiment, the multi-phase titanium oxide comprises a mixture of anatase TiO ₂ phase and rutile TiO ₂ phase.

In another embodiment, the n-type semiconductor is titanium oxide with a dopant. For example, the dopant can donate electrons to the conduction band of titanium oxide. In another embodiment, the n-type semiconductor is titanium oxide doped with N, C, or both. In another embodiment, n-type semiconductors, wherein _{(Ti 1-r M r)} (O 2-s-t C s N t) ( wherein, M is Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn, or Cu, or combinations thereof; r is in the range of 0 to 0.25; s is in the range of 0.001 to 0.1; t is 0.001. In the range of 0.1 to 0.1).

Another embodiment, a photocatalyst _{(Ti 0.99 Sn 0.01) (O} 2-s-t C s N t), (Ti 0.97 Sn 0 3) (O 2-s-t C s N t _{), (Ti 0.95 Sn 0.05)} (O 2-s-t C s N t), (Ti 0.90 Sn 0.10) (O 2-s-t C s N t), (Ti _{0.85 Sn 0.15) (O 2-} s-t C s N t), (Ti 0.985 Ni 0.015) (O 2-s-t C s N t), (Ti 0.98 Ni _{0.02) (O 2-s-} t C s N t), (Ti 0.97 Ni 0.03) (O 2-s-t CsNt), (Ti 0.99 Sr 0.01) (O 2 _−s−t CsNt), (Ti _0.97 Sr _0.03 ) (O _2−s−t CsNt), (Ti _0.95 Sr _0.05 ) (O _{2−s−t C s N t), (Ti} 0.97 Ba 0.03) (O 2-s-t C s N t), (Ti 0.95 Ba 0.05) (O 2-s-t C s N t ), (Ti _0.94 Sn _0.05 Fe _0.01 ) (O _2−s−t C _s N _t ), (Ti _0.94 Sn _0.05 Ni _0.01 ) (O _2−s−t C _s N _t ), (Ti _0.99 Fe _0.01 ) (O _2−s−t C _s N _t ), (Ti _0.95 Zn _0.05 ) (O _2−s−t C _s N _{t) ), (Ti 0.77 Sn 0.15 Cu} 0.08) (O 2-s-t C s N t), (Ti 0.85 Zn 0.15) (O 2-s-t C s N t _{), (Ti 0.90 Bi 0.10)} (O 2-s-t C s N t), (Ti 0.996 V 0.004) (O 2-s-t CsNt), (T _{0.984 V 0.016) (O 2-} s-t CsNt), (Ti 0.970 V 0.03) (O 2-s-t CsNt), (Ti 0.997 Mo 0.003) (O _{2-s-t C s N} t), (Ti 0.984 Mo 0.016) (O 2-s-t C s N t), (Ti 0.957 Mo 0.043) (O 2-s- _{t C s N t), (} Ti 0.97 W 0.03) (O 2-s-t C s N t), (Ti 0.95 W 0.05) (O 2-s-t C s N _{t), (Ti 0.996 V 0.004} ) (O 2-s-t C s N t), (Ti 0.984 V 0.016) (O 2-s-t C s N t) or ( Ti _0.970 V _0.03) containing _{(O 2-s-t C} s N t).

  Some embodiments include a method of degrading a compound comprising exposing the compound to a photocatalyst comprising a homogeneous material described herein in the presence of light. In some embodiments, the compound is a contaminant such as a volatile organic compound.

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

  Certain embodiments described herein include methods for introducing mixed valence compounds. The method includes adding a dispersant to the mixed valence compound to charge the surface of the n-type compound more positively; adding an attractant to the n-type compound to further increase the surface charge of the n-type semiconductor. Negatively charging; and mixing differently charged materials with each other at a temperature below the doping temperature of the mixed valence compound.

It is the schematic which shows the relationship between the conduction energy band regarding a metal material, and a valence energy band. It is the schematic which shows the relationship between the conduction energy band regarding a semiconductor material, and a valence energy band. It is the schematic which shows the relationship between the conduction energy band regarding a non-conductive material, and a valence energy band. FIG. 2 is a schematic diagram showing conduction and valence energy band levels for various compounds described herein.

FIG. 2 shows x-ray diffraction patterns of embodiments of p-type and n-type composite materials described herein, with n-type material only.

FIG. 4 shows x-ray diffraction patterns of another embodiment of the p-type and n-type composite materials described herein, along with the case of n-type material only. FIG. 4 shows x-ray diffraction patterns of another embodiment of the p-type and n-type composite materials described herein, along with the case of n-type material only.

FIG. 4 shows diffuse reflectance spectra comparing p-type and n-type composite material embodiments described herein with n-type material only (Ti (OCN) ₂ : Sn). FIG. 4 shows a diffuse reflectance spectrum comparing another embodiment of the p-type and n-type composite materials described herein with the n-type material alone (CeO ₂ ). FIG. 4 shows a diffuse reflectance spectrum comparing another embodiment of the p-type and n-type composite materials described herein with the n-type material alone.

2 is a graph showing the degradation of acetylaldehyde by various photocatalytic complexes described herein, Ex-1A and CE-1.

According to various photocatalytic complexes described herein, Ex-1A and CE-1, after exposure to 800 lux of visible light from a fluorescent lamp, E. coli. It is a graph which shows the antibacterial activity (CFU / specimen) with respect to Coli. According to various photocatalytic complexes described herein, Ex-4 and CE-2, after exposure to 800 lux of visible light from a fluorescent lamp, E. coli. It is a graph which shows the antibacterial activity (CFU / specimen) with respect to Coli.

According to the photocatalytic complex, Ex-1, before and after treatment for 7 days at 85 ° C. and 85% relative humidity (RH). 2 is a graph showing enhanced durable antimicrobial activity against Coli. According to the photocatalyst complex, Ex-7, before and after treatment at 300 ° C. for 20 minutes. 2 is a graph showing enhanced durable antimicrobial activity against Coli.

₂ is a graph showing natural blue dye discoloration with various photocatalytic complexes described herein, Example 1 and CE-1 with and without Cu _x O input with rutile TiO _2. .

2 is a graph showing the degradation of acetaldehyde by various photocatalytic complexes described herein, Ex-12, 13, 15, 16, and CE-6.

FIG. 6 is a graph showing the dye discoloration of a blue dye color by various photocatalytic complexes, Example 19, and SnO ₂ without input.

FIG. 5 is a graph showing natural blue dye discoloration with various photocatalytic complexes, Ex-18. FIG.

E. FIG. 6 is a graph showing the effect of a physical mixture of CE-0 (0.25 wt% CuO + 0.12 wt% Cu ₂ O + 0.5 wt% Sn-doped Ti (OCN) ₂ photocatalyst) on Coli killing properties.

FIG. 6 is a graph showing the effect of Ex-7A (alumina loaded with 0.5 wt% Cu _x O (non-photocatalyst)) on antibacterial properties (E. coli killing study). FIG. 6 is a graph showing the effect of Ex-1B (Sn doped Ti (OCN) 2 photocatalyst loaded with 0.5 wt% Cu _x O) on antibacterial properties (E. coli killing study). FIG. 5 is a graph showing the synergistic effect of Ex-1 (Sn doped Ti (OCN) ₂ loaded with 1 wt% Cu _x O) on antibacterial properties (E. coli killing study). FIG. 6 is a graph showing enhanced durability results for Ex-1 (Sn doped Ti (OCN) ₂ loaded with 1 wt% Cu _x O) versus antibacterial properties (E. coli killing study).

To antimicrobial _properties, it is a graph showing the synergistic effect of Cu x O / P25 and _{Cu x O / Al 2 O 3} (E.coli killing Research). FIG. 6 is a graph showing enhanced durability results for Cu _x O / P25 and Cu _x O / Al ₂ O ₃ versus antibacterial properties (E. coli killing study).

  The present disclosure describes a heterogeneous material having a p-type semiconductor comprising a mixed valence oxide compound. A p-type semiconductor has a p-type valence band. The heterogeneous material also includes an n-type semiconductor having an n-type valence band that is a valence band deeper than the p-type valence band. In the heterogeneous material, the n-type semiconductor communicates with the mixed valence oxide compound by ionic charge. These polyvalent heterogeneous materials can be used to increase the photocatalytic activity of the photocatalytic material and to improve durability (ie, maintain photocatalytic activity over time). The photocatalytic material is useful for having and / or enhancing antibacterial (light / dark) activity, antiviral activity, degradation of volatile organic compounds (VOC), and / or dye discoloration in aqueous solution.

  As shown in FIG. 1, the conduction band 10 has an electron energy sufficient to free an electron from bonding with its atoms and to move freely within the atomic lattice of the material as “delocalized electrons”. Range. In semiconductors, the valence band 20 is the highest range of electron energy in which electrons usually exist at an absolute zero temperature. Valence electrons are substantially bonded to individual atoms as opposed to conduction electrons (found in semiconductors) that can move more freely within the atomic lattice of the material. On the graph of the electronic band structure of the material, the valence band 20 is generally located below the conduction band and is separated from this conduction band in the insulator and semiconductor by a band gap 30. In some materials, the conduction band has substantially no discernable energy gap separating it from the valence band. The conduction and valence bands may actually overlap if the valence band level energy is negative or higher than the conduction band level energy (overlap 25).

  Various materials may be categorized by their band gap; for example, by the difference between the valence band 20 and the conduction band 10. In non-conductors (eg, insulators), the conduction band is much higher energy than the valence band, and therefore very much energy is used to displace the valence electrons of the insulator to effectively conduct electricity. Cost. These insulators are said to have non-zero band gaps. In conductors such as metals with many free electrons under normal circumstances, the conduction band 10 overlaps with the valence band 20 (25) —no band gap and thus additional applied energy to displace the valence electrons. Requires little or no. In a semiconductor, the band gap is small, about 200 nm to 1000 nm. While bound by theory, it requires relatively little energy (in the form of heat or light) to move semiconductor electrons from the valence band to another energy level and to conduct electricity. Therefore, it is named semiconductor.

In some embodiments, a p-type semiconductor comprising a mixed valence oxide compound, the compound having a p-type conduction band and a p-type valence band; and a p-type valence band Heterogeneous materials are provided, including individual n-type semiconductors having deeper, lower energy, or more negative n-type valence bands. The n-type semiconductor should communicate with the p-type semiconductor by ionic charge, which can transfer the ionic charge from the n-type semiconductor to the mixed valence oxide compound or from the mixed valence oxide compound to the n-type semiconductor. Means. Examples of suitable conduction and valence bands are shown in FIG. Without being bound by theory, if the valence band of an n-type semiconductor is deeper or more negative than the p-type valence band, the electrons can be more easily transferred from the n-type to the p-type compound. . When the material is in communication by ions, electrons can be transferred from one compound to the next, allowing regeneration from a higher valence compound to a lower valence compound. For example, Cu ²⁺ can be recycled to Cu ¹⁺ via this mechanism. In some embodiments, the materials that are in communication by ions are input to each other. By loading, the materials retain their separate identities; for example, Cu _x O (p-type semiconductor) is separated from TiO ₂ , Ti (OCN) ₂ : Sn, etc. (n-type semiconductor). In certain embodiments, one material is on the surface, in contact with or in close proximity to the other material, and is physically separated from the other material as opposed to doping, and the ionic charge is simply Separated or mixed (physical mixing). In some embodiments, such contact and / or isolation can be determined by transmission electron microscopy (TEM) inspection of p-type and n-type materials. In other embodiments, the heterogeneous material is integrated into the compound matrix; for example, incorporated into the compound / crystal lattice.

The heterogeneous material may comprise any suitable p-type semiconductor, including any semiconductor whose charge carriers are effectively holes. These holes may be present in the p-type valence band, which can be essentially filled with electrons, except for a few holes that can inherently carry a positive charge. In some embodiments, the p-type semiconductor may include a mixed valence oxide compound having a p-type valence band. In some embodiments, the mixed valence oxide compound is a mixed valence pair of the same metal element, such as copper (I) and copper (II); cobalt (II) and cobalt (III); Mn (II) and Mn (III); Fe (II) and Fe (III); and / or Ir (III) and Ir (IV); and combinations thereof. In certain embodiments, the copper (I) and copper (II) compounds can be Cu _x O compounds. In certain embodiments, the mixed valence oxide compound can include Cu ¹⁺ and Cu ²⁺ . The ratio of the mixed valence oxide compound can be from 10% to 90%, from 90% to 10%. Specific ratios are: 15% to 85%; 20% to 80%; 25% to 75%; 30% to 70%; 35% to 65%; 40% to 60%; 45% to 55%; 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 mixed valence metal oxide compound is Cu ¹⁺ : Cu ²⁺ with a ratio of Cu ^{1+ from} 10% to 90% to Cu ^{2+ from} 90% to 10%. The ratio of Cu ¹⁺ : Cu ²⁺ is 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 65%: 35%; about 70%: 30%; about 75%: 25%; about 80%: 20%; or about 85%: 15%. In some embodiments, the ratio is Cu ¹⁺ : Cu ²⁺ wt%. In some embodiments, the ratio is Cu ¹⁺ : Cu ²⁺ mol%.

  In some embodiments where the n-type semiconductor is in ionic charge with the p-type semiconductor, the p-type semiconductor is injected into the n-type semiconductor. In some embodiments where the n-type semiconductor is in ionic charge communication with the p-type semiconductor, the p-type semiconductor can be embedded, layered, contacted, and / or deposited in the n-type semiconductor. . In some embodiments, the p-type semiconductor mixed valence compound is substantially uniformly dispersed on the n-type semiconductor. The particle size of the mixed valence compound is less than 200 nm; less than 190 nm; less than 180 nm; less than 170 nm; less than 160 nm; less than 150 nm; less than 140 nm; less than 130 nm; Less than 60 nm; less than 50 nm; less than 40 nm; less than 30 nm; less than 20 nm; or less than 10 nm. In certain embodiments, the particle size of the mixed valence compound is 100 nm or less.

  In some embodiments, the p-type semiconductor comprises 0.001 to 10% by weight of the heterogeneous material and the n-type semiconductor comprises 99.999 to 90% by weight of the heterogeneous material. In additional embodiments, the p-type semiconductor comprises 0.001% by weight of heterogeneous material; 0.005% by weight of heterogeneous material; 0.01% by weight of heterogeneous material; 0.05% by weight of heterogeneous material. 0.1% by weight of heterogeneous material; 0.5% by weight of heterogeneous material; 1% by weight of heterogeneous material; 2% by weight of heterogeneous material; 3% by weight of heterogeneous material; 5% by weight of heterogeneous material; 6% by weight of heterogeneous material; 7% by weight of heterogeneous material; 8% by weight of heterogeneous material; 9% by weight of heterogeneous material; or 10% by weight of heterogeneous material Make up%. In additional embodiments, the n-type semiconductor comprises 90% by weight of the heterogeneous material; 91% by weight of the heterogeneous material; 92% by weight of the heterogeneous material; 93% by weight of the heterogeneous material; 94% by weight of the heterogeneous material. 95% by weight of heterogeneous material; 96% by weight of heterogeneous material; 97% by weight of heterogeneous material; 98% by weight of heterogeneous material; 99% by weight of heterogeneous material; 99.1% by weight of heterogeneous material 99.2% by weight of the heterogeneous material; 99.3% by weight of the heterogeneous material; 99.4% by weight of the heterogeneous material; 99.5% by weight of the heterogeneous material; 99.6% by weight of the heterogeneous material Constitutes 99.7% by weight of the heterogeneous material; 99.8% by weight of the heterogeneous material; or 99.5% by weight of the heterogeneous material.

In some embodiments, the p-type semiconductor is a mixture of copper oxides, such as a first copper oxide compound and a second copper oxide, such as a Cu (I) compound (eg, Cu ₂ O) and a Cu (II) compound. (Eg, a mixture with CuO). In some embodiments, the p-type semiconductor comprises Cu (I) (eg, Cu ₂ O) and Cu (II) (eg, CuO) from about 1: 9 to about 3: 7, from about 1: 3. About 1: 6, or about 1: 3 to about 1: 4 in a weight: weight or mole: molar ratio [Cu (I): Cu (II)].

Some embodiments are n-type, wherein the p-type semiconductor of the previous paragraph is titanium oxide doped with tin or titanium oxide such as Ti (O, C, N) ₂ or TiO ₂ having multiple phases. Includes in combination with semiconductors. In some embodiments, such TiO ₂ can have two phases, such as rutile TiO ₂ and anatase TiO ₂ . In some embodiments, the n-type semiconductor comprises from about 70% to about 90% anatase phase and 10% to about 30% rutile phase TiO ₂ , from about 80% to about 90% anatase phase and 20%. About 30% rutile TiO ₂ , about 75% to about 80% anatase phase and 15% to about 20% rutile TiO ₂ , or about 83% anatase TiO ₂ and 17% rutile phase TiO ₂ . Some embodiments include the p-type semiconductor of the previous paragraph in combination with an n-type semiconductor that is tin oxide.

A semiconductor comprising a p-type semiconductor having a mixture of copper oxides and an n-type semiconductor that is titanium oxide doped with tin or titanium oxide such as Ti (O, C, N) ₂ or TiO ₂ having a plurality of phases. In some embodiments, the copper oxide is about 0.1% to about 5%, about 0.2% to about 2%, about 0.2% to about 1.% of the total weight of the n and p-type semiconductors. It may be 5%, about 0.5%, or about 1%.

In some embodiments, the p-type semiconductor is injected into the n-type semiconductor. In some embodiments, the n-type semiconductor is of cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, or aluminum having a valence band deeper than that of the p-type semiconductor valence band. An oxide containing an element that can be converted into an oxide. In some embodiments, the n-type semiconductor can be anatase, rutile, wurtzite, spinel, perovskite, pyrochlore, garnet, zircon, and / or tialite phase material, or mixtures thereof. Each of these options is given its ordinary meaning as understood by those skilled in the semiconductor arts. Comparison of the x-ray diffraction patterns of a given standard and generated sample is one of several methods that may be used to determine whether a sample contains a particular phase. Exemplary standards include the National Institute of Standards and Technology (NIST) (Gaitherburg, Maryland, USA) and / or the International Diffraction and Diffraction IC (the International Center for Diffraction and Diffraction). XRD spectra provided by The Joint Committee on Powder Diffraction Standards [JCPDS] (Newtown Square, Pennsylvania, USA). In some embodiments, the perovskite can be a perovskite oxide. In some embodiments, the perovskite oxide is FeTiO ₃ , YFeO ₃ , LuRhO ₃ , BaSnO ₃ , Ba _0.8 Ca _0.2 TiO ₃ , CdSnO ₃ , LaRhO ₃ , LaRhO ₃ , LaMnO ₃ , LaMnO ₃ , _{CuTiO 3, MgTiO 3, ZnTiO 3} , BiNb 1-x Ta x O 4 ( where the x = 0 1.00), or _{InNb 1-x Ta x O 4} ( where x = 0 1.00 ) Can be included.

In additional embodiments, the n-type semiconductor may include oxides of cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, niobium, vanadium, iron, cadmium, germanium, and / or aluminum. it can. n-type semiconductors are 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 Ta _{v Nb 1-v O 7;} 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 _{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 , wherein A is , Sr, Ba, or combinations thereof); CuMnO ₂ ; PbWO ₄ ; CuFeO ₂ ; InVO ₄ ; MVWO _{6 where} M can be Li, Ag, or a combination thereof ); Bi ₂ MNbO ₇ , where M can be Al, Ga, In, Y, rare earth, Fe, or combinations thereof Zr ₂ WO ₆ ; PbWO ₄ ; SnWO ₄ ; Bi ₂ W ₂ O ₉ ; Na ₂ W ₄ O ₁₃ ; and / or MWO ₄ (wherein M is Ca, Zn, Cu, or combinations thereof) Can also be included).

In some embodiments, the n-type semiconductor can be a vanadium garnet semiconductor photocatalyst. In some embodiments, the vanadium garnet semiconductor photocatalyst is represented by the formula: (A _1-x O _x ) ₃ (M) ₂ (V ₃ ) O ₁₂ , where 0 <x <1. Can do. In some embodiments, the accumulated ionic charge of (A _1-x O _x ) ₃ and (M) ₂ is +9. In some embodiments, A ⁺ is Li ⁺ , Cu ⁺ , Na ⁺ , K ⁺ , Ti ⁺ , Cd ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Y ³⁺ , Bi ³⁺ , Ln ³⁺ , or these It can be a combination. In some embodiments, M is Li ⁺ , Ni ²⁺ , Mg ²⁺ , Co ²⁺ , Cu ²⁺ , Zn ²⁺ , Mn ²⁺ , Cd ²⁺ , Cr ³⁺ , Fe ³⁺ , or Sc ³⁺ , or combinations thereof, It can be one or either.

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

In some embodiments, the n-type semiconductor can be a mixed titanate. The term “mixed titanate” refers to a compound comprising Ti, O, and at least another element; for example, Ca, Cu, Mg, or La. In some embodiments, the mixed titanate is CaCu ₂ Ti ₃ O ₁₂ (perovskite titanate); MgTi ₂ O ₅ (pseudoplate titanite); and / or La ₂ Ti ₂ O ₇ (pyrochlorite titanate). be able to. In some embodiments, the oxidized Ti can comprise a mixture of anatase and rutile TiO ₂ .

In some embodiments, the n-type semiconductor can include mixed copper oxide. Mixed copper oxide refers to an n-type semiconductor containing Cu, O and another element different from copper and oxygen. In some embodiments, the mixed oxidized Cu can be CuMnO ₂ or CuFeO ₂ .

In some embodiments, the n-type semiconductor can be a single or mixed ferrite. In some embodiments, the mixed ferrite is α-Fe ₂ O ₃ ; MFe ₂ O ₄ (wherein M is Mg, Zn, Ca, Ba, or combinations thereof); Ca ₂ Fe ₂ O ₅ , MFe ₁₂ O ₁₉ (wherein M is Sr, Ba, or a combination thereof); Sr ₇ Fe ₁₀ O ₂₂ , MFeO _{2.5 + x} (wherein M is Sr, Ba, 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 an oxynitride semiconductor photocatalyst doped with Cu _x O. In some embodiments, the oxynitride semiconductor photocatalyst is TaON; MTaO ₂ N (wherein M is Ca, Sr, Ba, 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) can contain.

In some embodiments, the n-type semiconductor can be a sulfide, selenide, or sulfoselenide semiconductor photocatalyst loaded with Cu _x O. In some embodiments, a sulfide, selenide or sulfoselenide compound semiconductor photocatalyst, _{is, Cd (S y, Se 1} -y) ( where, 0 <y <a 1); (Cd, Zn ( S y , 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 1} , Se _1-y ) ₂ (where 0 <y <1); and / or Sm ₂ Ti ₂ S ₂ O ₅ .

In certain embodiments, n-type semiconductors, wherein _{Al 2-x In x TiO 5} ( wherein, x is in the range from 0 to 2 (0 <x <2) ) containing a compound represented by the. In other specific embodiments, the n-type semiconductor comprises a compound represented by the formula Zr _1-y Ce _y TiO ₄ , wherein y is in the range of 0 to 1 (0 <y <1). Including. In certain embodiments, the n-type semiconductor is titanium oxide having a valence band controlled through doping. In some embodiments, the n-type semiconductor is titanium oxide doped with N or C or both. In some embodiments, titanium oxide has the formula _{(Ti 1-r M r)} (O 2-s-t C s N t) ( wherein, M represents, Sn, Ni, Sr, Ba , Fe, Bi , V, Mo, W, Zn, Cu, or combinations thereof; r is in the range of 0 to 0.25; s is in the range of 0.001 to 0.1; t is from 0.001 In the range of 0.1). In some embodiments, r is 0.20 or less. In some embodiments, r is more particularly 0; 0.01; 0.02; 0.03; 0.04; 0.05; 0.06; 0.07; 0.08; 0.1; 0.13; 0.14; 0.15; 0.16; 0.17; 0.18; 0.19; 0.20; 0.21; 0.22; 0.23; 0.24; or 0.25. In some embodiments, s is more particularly 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 some embodiments, t is more particularly 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.

The material is also described in co-pending and commonly assigned application No. 13 / 741,191 filed Jan. 14, 2013, which is incorporated by reference in its entirety with respect to its description of photocatalytic compounds and / or compositions. Has been. In some embodiments, M is Sn, Ni, Sr, Ba, Fe, Bi, or combinations thereof. In some embodiments, r is in the range of 0.0001 to 0.15. In some embodiments, M is Sn. In some embodiments, r is at least 0.001. In some embodiments, the n-type semiconductor is (Ti _0.99 Sn _0.01 ) (O _2−s−t CsNt), (Ti _0.97 Sn _0.03 ) (O _2−s−t C). _{s N t), (Ti 0.95} Sn 0.05) (O 2-s-t C s N t), (Ti 0.90 Sn 0.10) (O 2-s-t C s N t) _{, (Ti 0.85 Sn 0.15) (} O 2-s-t C s N t), (Ti 0.985 Ni 0.015) (O 2-s-t 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-s-} t C s N t), (Ti 0.97 Sr 0.03) (O 2-s-t C s N t), (Ti 0.95 Sr _{.05) (O 2-s-} t C s N t), (Ti 0.97 Ba 0.03) (O 2-s-t C s N t), (Ti 0.95 Ba 0.05) ( _{O 2-s-t C s} N t), (Ti 0.94 Sn 0.05 Fe 0.01) (O 2-s-t C s N t), (Ti 0.94 Sn 0.05 Ni 0 _{.01) (O 2-s-} t C s N t), (Ti 0.99 Fe 0.01) (O 2-s-t C s N t), (Ti 0.95 Zn 0.05) ( _{O 2-s-t C s} N t), (Ti 0.77 Sn 0.15 Cu 0.08) (O 2-s-t C s N t), (Ti 0.85 Zn 0.15) ( _{O 2-s-t C s} N t), (Ti 0.90 Bi 0.10) (O 2-s-t C s N t), (Ti 0.996 V 0.004) (O 2 _{s-t C s N t)} , (Ti 0.984 V 0.016) (O 2-s-t C s N t), (Ti 0.970 V 0.03) (O 2-s-t C _{s N t), (Ti 0.997} Mo 0.003) (O 2-s-t C s N t), (Ti 0.984 Mo 0.016) (O 2-s-t C s N t) , (Ti _0.957 Mo _0.043 ) (O _2−s−t C _s N _t ), (Ti _0.97 W _0.03 ) (O _2−s−t C _s N _t ), and / or (Ti _0.95 W _0.05 ) (O _2−s−t C _s N _t ). In some embodiments, the n-type semiconductor is (Ti _0.996 V _0.004 ) (O _2−s−t C _s N _t ), (Ti _0.984 V _0.016 ) ( _{O 2 −s−} ). _t C _s N _t ), and / or (Ti _0.970 V _0.03 ) (O _2−s−t C _s N _t ).

In some embodiments, where the heterogeneous material includes a p-type semiconductor loaded into an n-type semiconductor, the heterogeneous material further includes a second n-type semiconductor, wherein at least a portion of the second n-type semiconductor is: It is an ionic charge isolated from a p-type semiconductor. In some embodiments, at least a portion of the second n-type semiconductor is physically separated from the p-type semiconductor and the ionic charge is isolated, mixed, and / or not injected from the p-type semiconductor. be able to. In some embodiments, the second n-type semiconductor can be any of the n-type semiconductors as described elsewhere in this application. In some embodiments, an n-type semiconductor with isolated or mixed ionic charges can include CeO ₂ and / or a multi-phase n-type semiconductor compound. In some embodiments, the multi-phase n-type semiconductor compound comprises an anatase phase and a rutile phase compound. In some embodiments, the multi-phase n-type semiconductor compound can be titanium oxide. In some embodiments, the anatase phase can be 2.5% to about 97.5%, 5% to about 95%, and / or about 10% to about 90%; .5% to about 2.5%, 95% to about 5%, and / or about 10% to about 90%. Non-limiting examples of suitable materials include TiO ₂ mixtures sold under the trade name P25 (83% anatase phase TiO ₂ + 17% rutile phase TiO ₂ ) sold by Evonik, However, the present invention is not limited to this. In some embodiments, the n-type semiconductor physically mixed with the p-type input to WO ₃ can include CeO ₂ , TiO ₂ , SrTiO ₃ , and / or KTaO ₃ . In some embodiments, the n-type semiconductor physically mixed with the p-type injected into the multi-phase n-type semiconductor compound (eg, P25) is a non-input type multi-phase n-type semiconductor compound (eg, P25). In some embodiments, the n-type semiconductor physically mixed with the p-type loaded into the multi-phase n-type semiconductor compound may include CeO ₂ , TiO ₂ , SrTiO ₃ , and / or KTaO _3. it can. 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 oxide including CeO ₂ or TiO ₂ . In some embodiments, the n-type semiconductor comprises 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 . be able to.

In some embodiments, the n-type semiconductor is RE _k E _m O _n , where RE is a rare earth element, E is an element or combination of elements, O is oxygen, and 1 ≦ k ≦ 2, 2 ≦ m ≦ 3, and 0 ≦ n ≦ 3). In some embodiments, the n-type semiconductor is RE _p O _{q where} RE can be a rare earth metal and p can be between 1 and 2, or between 1 and 2 Q can be greater than or equal to 2 and less than or equal to 3, or between 2 and 3. Examples of suitable rare earth elements include scandium, yttrium, and lanthanide and actinide series elements. Lanthanide elements include elements with atomic numbers 57 to 71. Actinide elements include elements with atomic numbers 89 to 103. In some embodiments, the n-type semiconductor can be Ce _x Zr _y O ₂ , where the y / x ratio = 0.001 to 0.999. In some embodiments, the n-type semiconductor can be cerium. In some embodiments, the n-type semiconductor can be CeO _a (a ≦ 2). In some embodiments, the n-type semiconductor can be cerium oxide (CeO ₂ ).

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

In some embodiments, the molar ratio of the physical mixture of the n-type semiconductor (eg, CeO ₂ ) and the WO ₃ (eg, Cu _x O—WO ₃ ) into which the p-type semiconductor is loaded is n-type semiconductor 0. It can be set to 100% to 1% for p-type semiconductor (WO ₃ with Cu _x O added) to 99%. In some embodiments, the molar ratio of the physical mixture of n-type semiconductor (eg, CeO ₂ ) and WO ₃ loaded with p-type semiconductor is 25-75% n-type semiconductor (and everything in between) N-type material (eg, WO ₃ ) loaded with p-type semiconductor can be 75% to 25% (and all integers between them). In some embodiments, the molar ratio of the physical mixture of n-type semiconductor (eg, CeO ₂ ) and WO ₃ loaded with p-type semiconductor is 40 to 60% (and all between them) ) Vs. n-type material (eg, WO ₃ ) loaded with p-type semiconductor can be 60% to 40% (and all integers in between).

  In some embodiments, the heterogeneous material can further include a noble metal in communication with the mixed valence oxide compound by ionic charge. In some embodiments, the noble metal is input into an n-type semiconductor. In some embodiments, the noble metal can be, but is not limited to, rhodium, ruthenium, palladium, silver, osmium, platinum, and / or gold, or mixtures thereof. In one embodiment, the noble metal is platinum.

  In some embodiments, the method for introducing the mixed valence compound is to add a p-type precursor to the attractant to make the surface charge of the n-type semiconductor more negative, where p The mold precursor includes a copper cation complex. In some embodiments, the method for introducing a mixed valence compound comprises adding an attractant to the n-type compound; and lowering the n-type and p-type precursors below the mixed valence compound doping temperature. Combining with each other at temperature. In some embodiments, the method further includes adding a dispersant to the n-type compound to more positively charge the surface of the n-type compound.

  In some embodiments, the method for introducing a mixed valence compound comprises adding a dispersant to the n-type compound to make the surface of the n-type compound more positively charged; The p-type precursor contains a copper cation complex; an attractant is added to the n-type compound to make the surface charge of the n-type semiconductor more negative. And differently charged materials can be combined with each other at a temperature lower than the doping temperature of the mixed valence compound.

  In some embodiments, the dispersant can be a strong acid. In some embodiments, the dispersant can be 4-7M HCl. In some embodiments, the dispersant is 6M HCl.

  In some methods, a valence control material is added with a differently charged material to control the mixed valence oxide during the synthesis of the mixed valence oxide. In some embodiments, the valence control material is a slow reducing agent. In some embodiments, the valence control material can be at least one of a sugar, a hydrazide, an amino acid, and / or an amide. In some embodiments, the amide can be urea. In some embodiments, the sugar can be sucrose, fructose, and / or glucose. In some embodiments, the sugar is glucose. In some embodiments, the hydrazide can be carbohydrazide, oxalyl dihydrazide, maleic hydrazide, diformyl hydrazide, or tetraformyl trisazine. In some embodiments, the amino acid can be at least one proteinogenic or naturally occurring amino acid. In some embodiments, the amino acid can be an aliphatic amino acid (eg, glycine, alanine, valine, leucine, and / or isoleucine). In some embodiments, the amino acid can be a hydroxyl or sulfur containing amino acid (eg, serine, cysteine, threonine, and / or methionine). In some embodiments, the amino acid can be cyclic (eg, proline). In some embodiments, the amino acid can be aromatic (eg, phenylalanine, tyrosine, and / or tryptophan). In some embodiments, the amino acid can be basic (eg, histidine, lysine, and / or arginine). In some embodiments, the amino acid is acidic or amide (eg, aspartate, glutamate, asparagine, and / or glutamine). In some embodiments, the amino acid can be selenocysteine and / or pyrrolysine. In some embodiments, the amino acid can be non-proteinogenic. In some embodiments, non-proteinogenic amino acids include those not found in proteins (eg, carnitine, GABA). In some embodiments, non-proteinogenic amino acids can be in isolation by standard cellular mechanisms (eg, hydroxyproline and selenomethionine). In some embodiments, the amino acid is soluble in water. In some embodiments, the amino acid is soluble in 90 ° C. water. In some embodiments, the amino acid is substantially totally soluble in 90 ° C. water. The term soluble has the usual meaning known to those skilled in the art.

In some embodiments, the ratio of mixed valence oxide compounds, such as Cu ¹⁺ compounds and Cu ²⁺ compounds, can be controlled by the method of introducing Cu into the p-type semiconductor, including the addition of attractants. In some embodiments, attractants that can control the ratio of mixed valence oxide compounds can include monosaccharides and base compounds. In some embodiments, the monosaccharide can be glucose. In some embodiments, the glucose can be D-glucose and / or L-glucose. In some embodiments, the glucose to NaOH ratio can be from 10% to 90%, from 90% to 10%. Specific ratios include: 15% to 85%; 20% to 80%; 25% to 75%; 30% to 70%; 35% to 65%; 40% to 60%; 45% to 55%; Include% to 50%; 55% to 45%; 60% to 40%; 65% to 35%; 70% to 30%; 75% to 25%; 80% to 20%; and 85% to 15% You can also. In some embodiments, the base can be NaOH. The valence of the Cu _x O compound is chemically controlled.

  In some embodiments, the attractant can be an agent that provides a sufficient amount of hydroxyl ions to bring the pH of the entire solution between pH 8.0 and pH 9.0. In some embodiments, the attractant can be a strong base. In some embodiments, the attractant is a 4-7M strong base. In some embodiments, the attractant is 6M NaOH.

In some embodiments, the p-type precursor can be a substantially sodium free compound. In some embodiments, the substantially sodium free compound can be a copper cation complex. In some embodiments, the copper cation complex is bis (ethylenediamine) copper (II) (BEDCuII), tetraamine copper chloride (II), tetraamine copper sulfate (II), and / or tetraamine copper hydroxide (II), And / or a mixture thereof. In some embodiments, the compound can be bis (ethylenediamine) copper (II). The structure of BEDCuII is shown below.

  In some embodiments, the doping temperature of the mixed valence compound is between 150 ° C. and 700 ° C. In some embodiments, the mixed valence compound below the doping temperature is less than 175 ° C, less than 150 ° C, less than 125 ° C. In some embodiments, the mixing temperature is between 75 ° C and 125 ° C. In some embodiments, the mixing temperature is 80 ° C; 85 ° C; 95 ° C; 100 ° C; 105 ° C; 110 ° C; 115 ° C;

  In some embodiments, the precursor selected for the p-type semiconductor is a salt of chloride, acetate, nitrate, sulfate, carbonate, oxide, hydroxide, peroxide, or combinations thereof. It can be.

  In some embodiments, the described heterogeneous material has photocatalytic activity. Heterogeneous materials can be antibacterial (light and dark); antiviral; can degrade volatile organic compounds (VOC); and / or can discolor food additive dyes. Suitable non-limiting examples of food additive dyes include Natural Blue Colored powder (Color Maker, Anaheim, California, USA) and / or FD & C Blue No. 2 Synthetic food additive dyes Food additive dyes (synthetic blue powder, Chromatech, Inc., Michigan, USA). The heterogeneous materials described herein can also increase the durability (time of effectiveness) of the photocatalytic material.

  One skilled in the art knows how to determine whether a heterogeneous material is antibacterial (bright), for example after the heterogeneous material has been exposed to visible light. In one embodiment, the antimicrobial exposure is at least 10% reduction (90% survival), at least 50% reduction (50% survival), at least 99% reduction (at least 1% survival), at least 99.9. % Reduction (at least 0.1% residual), or at least 100% reduction (0% residual). One example of determining whether a heterogeneous material is antibacterial (bright) can be by assessing the amount of bacteria present; for example, if the heterogeneous material contacts the bacteria and After exposure to visible light, the reduction in the amount of bacteria present is assessed. For example, the amount of bacteria present in a sample after exposing the sample for a predetermined time can be assessed. In some embodiments, the sample can be exposed for 15 minutes, 30 minutes, 1 hour, 2 hours, 5 hours, 7.5 hours, 10 hours, 12 hours, 24 hours. In some embodiments, the sample is exposed to 800 lux from a fluorescent light source or at least 5 mW / cm 2 from a blue LED.

  Those skilled in the art are aware of methods for determining whether a heterogeneous material is antibacterial (dark). In one embodiment, the antimicrobial exposure is at least 10% reduction (90% survival), at least 50% reduction (50% survival), at least 99% reduction (at least 1% survival), at least 99.9. % Reduction (at least 0.1% residual), or at least 100% reduction (0% residual). One example of determining whether a heterogeneous material is antibacterial (dark) can be by assessing the amount of bacteria present, for example, exposure of the heterogeneous material to visible light. The reduction or reduction in the number of colonies present is assessed after contact with bacteria without.

  Those skilled in the art are aware of methods for determining whether a heterogeneous material is antiviral. One example of determining whether a heterogeneous material is antiviral can be, for example, by assessing inhibition or reduction of the number of viral (phage) colonies. In one embodiment, the determination of whether a heterogeneous material is antiviral can be by counting the number of viral colonies present over time after exposure to the heterogeneous material. . In one embodiment, the antiviral exposure is at least 10% reduction (90% residual), at least 50% reduction (50% residual), at least 99% reduction (at least 1% residual), at least 99. This results in a 9% reduction (at least 0.1% residual), or at least 100% reduction (0% residual).

Those skilled in the art know how to determine whether a heterogeneous material decomposes volatile organic compounds. One example of determining whether a heterogeneous material decomposes volatile organic compounds can be by evaluating the decomposition of organic compounds under electromagnetic radiation, eg, visible light. In one embodiment, determining the degradation of acetaldehyde as a reduction or% of initial degradation is an optional method of determining the degradation of volatile organic compounds; for example, ranging from 0% to 90% over time; Or it takes 3 to 10 hours or 5 hours under a certain amount of visible light, such as a 455 nm blue light emitting LED with a power of 270 mW / cm ² . In some embodiments, the degradation is at least 50%, 60%, 70%, 80%, 90%, or 100% of the initial amount of acetylaldehyde after exposure to the heterogeneous material.

  Those skilled in the art know how to determine whether a heterogeneous material discolors a food additive or pigment. One example of determining the color change of the food additive dye may be due to a decrease or percentage of the initial amount of food dye additive over time. In one example, the food additive can be a natural anthocyanin food additive dye or an FDC food additive dye. In some embodiments, the color change of the food dye additive can be 0% to 60% after 5 hours under a blue LED emitting at 455 nm with a power of 45 mW / cm 2. In some embodiments, the degradation is at least 25%, 30%, 40%, 50%, and / or 60% of the initial amount of natural anthocyanin food additive pigment after exposure to a heterogeneous material.

  Those skilled in the art are aware of how to determine whether a heterogeneous material is active over time; for example, whether to maintain the durability of the heterogeneous material. In some embodiments, the color change of the food dye additive decreased from zero to 60% after 5 hours under a blue LED emitting at 455 nm with a power of 45 mW / cm 2. For example, in some embodiments, retention of antimicrobial activity is after exposure to 85% relative humidity and 85 ° C. for at least 7 days.

(Embodiment 1)
A p-type semiconductor comprising a first metal oxide compound and a second metal oxide compound, wherein the first metal oxide compound and the second metal oxide compound have different oxidation states of the same metal. A p-type semiconductor having a p-type valence band;
An inhomogeneous material comprising an n-type semiconductor having an n-type valence band deeper than the p-type valence band and communicating with the p-type semiconductor by ionic charges.
(Embodiment 2)
The heterogeneous material of embodiment 1, further comprising a noble metal in communication with the first metal oxide compound and the second metal oxide compound by ionic charge.
(Embodiment 3)
The heterogeneous material of embodiment 2, wherein the noble metal is rhodium, ruthenium, palladium, silver, osmium, platinum, or gold.
(Embodiment 4)
The heterogeneous material according to embodiment 2 or 3, wherein the noble metal is introduced into 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 an ionic charge isolated from the p-type semiconductor.
(Embodiment 6)
Embodiment 6. The heterogeneous material of embodiment 5, wherein the second n-type semiconductor comprises cerium oxide.
(Embodiment 7)
The cerium oxide is CeO _2, heterogeneous material embodiment 6.
(Embodiment 8)
Embodiment 6. The heterogeneous material of embodiment 5, wherein the second n-type semiconductor comprises multi-phase TiO ₂ .
(Embodiment 9)
The first metal oxide compound includes copper (I) and the second metal oxide compound includes copper (II), the first metal oxide compound includes cobalt (II) and the first The second metal oxide compound includes cobalt (III), the first metal oxide compound includes Mn (II), and the second metal oxide compound includes Mn (III), The metal oxide compound includes Fe (II) and the second metal oxide compound includes Fe (III), or the first metal oxide compound includes Ir (III) and the second metal Embodiment 9. A heterogeneous material according to embodiment 1, 2, 3, 4, 5, 6, 7 or 8, wherein the oxide compound comprises Ir (IV).
(Embodiment 10)
The heterogeneous material of embodiment 1, 2, 3, 4, 5, 6, 7, 8 or 9 wherein the p-type semiconductor is introduced into 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 on 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 in the form of particles having a particle size of 100 nm or less.
(Embodiment 13)
The heterogeneous material of claim 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)
Embodiment 15. The heterogeneous material of embodiment 14, wherein the Cu _x O is chemically valence controlled.
(Embodiment 16)
The heterogeneous material of embodiment 9, wherein the ratio of copper (I): copper (II) is between 10:90 and 30:70.
(Embodiment 17)
Embodiments 1, 2, 3, wherein the p-type semiconductor is 0.001 to 10% by weight of the heterogeneous material and the n-type semiconductor is 90 to 99.999% by weight of the heterogeneous material 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 heterogeneous material.
(Embodiment 18)
Embodiment 1, 2, 3, 4, 5, 6, 7, 8, wherein said n-type semiconductor is an oxide of cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, or aluminum 9, 10, 11, 12, 13, 14, 15, 16 or 17 heterogeneous material.
(Embodiment 19)
The n-type _{semiconductor, 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 Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, ₁₂ , ₁₃ comprising In ₂ TiO ₅ , Al ₂ TiO ₅ , or LiCa ₂ Zn ₂ V ₃ O ₁₂ , 14, 15, 16 or 17 heterogeneous material.
(Embodiment 20)
Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, wherein the n-type semiconductor is Al _2-x In _x TiO ₅ (where 0 <x <2) 12, 13, 14, 15, 16 or 17 heterogeneous material.
(Embodiment 21)
Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, wherein the n-type semiconductor is Zr _1-y Ce _y TiO ₄ (where 0 <y <1) 12, 13, 14, 15, 16 or 17 heterogeneous material.
(Embodiment 22)
Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 wherein the n-type semiconductor is titanium oxide having a valence band controlled through doping 15, 16, or 17 heterogeneous material.
(Embodiment 23)
Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 wherein the n-type semiconductor is titanium oxide doped with N, C, or both 15, 16, or 17 heterogeneous material.
(Embodiment 24)
The n-type semiconductor, wherein _{(Ti 1-r M r)} compounds represented by _{(O 2-s-t C} s N t) ( in the formula,
M is Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn, Cu, or combinations thereof;
r is from 0 to 0.25;
s is 0.001 to 0.1,
t is 0.001 to 0.1)
23. The heterogeneous material of embodiment 22 which is titanium oxide comprising
(Embodiment 25)
_{(Ti 0.99 Sn 0.01) (O} 2-s-t C s N t), (Ti 0.97 Sn 0.03) (O 2-s-t C s N t), (Ti 0. _{95 Sn 0.05) (O 2-} s-t C s N t), (Ti 0.90 Sn 0.10) (O 2-s-t C s N t), (Ti 0.85 Sn 0. _{15) (O 2-s-} t C s N t), (Ti 0.985 Ni 0.015) (O 2-s-t C s N t), (Ti 0.98 Ni 0.02) (O _{2-s-t C s N} t), (Ti 0.97 Ni 0.03) (O 2-s-t CsNt), (Ti 0.99 Sr 0.01) (O 2-s-t CsNt) _{, (Ti 0.97 Sr 0.03) (} O 2-s-t CsNt), (Ti 0.95 Sr 0.05) (O 2-s-t C s N t), ( _{i 0.97 Ba 0.03) (O 2} -s-t C s N t), (Ti 0.95 Ba 0.05) (O 2-s-t C s N t), (Ti 0.94 _{Sn 0.05 Fe 0.01) (O 2} -s-t C s N t), (Ti 0.94 Sn 0.05 Ni 0.01) (O 2-s-t C s N t), ( _{Ti 0.99 Fe 0.01) (O 2} -s-t C s N t), (Ti 0.95 Zn 0.05) (O 2-s-t C s N t), (Ti 0.77 _{sn 0.15 Cu 0.08) (O 2} -s-t C s N t), (Ti 0.85 Zn 0.15) (O 2-s-t C s N t), (Ti 0.90 _{Bi 0.10) (O 2-s} -t C s N t), (Ti 0.996 V 0.004) (O 2-s-t CsNt), (Ti 0.984 V 0. _{016) (O 2-s-} t C s N t), (Ti 0.970 V 0.03) (O 2-s-t C s N t), (Ti 0.997 Mo 0.003) (O _{2-s-t C s N} t), (Ti 0.984 Mo 0.016) (O 2-s-t C s N t), (Ti 0.957 Mo 0.043) (O 2-s- _{t C s N t), (} Ti 0.97 W 0.03) (O 2-s-t C s N t), (Ti 0.95 W 0.05) (O 2-s-t C s N _{t), (Ti 0.996 V 0.004} ) (O 2-s-t C s N t), (Ti 0.984 V 0.016) (O 2-s-t C s N t), or (Ti _0.970 V _0.03 ) (O _2−s−t C _s N _t )
25. The heterogeneous material of embodiment 24, comprising:
(Embodiment 26)
The n-type _{semiconductor, (Ti 1-r M r} ) (O 2-s-t C s N t)
(Where
M is Sn,
r is from 0 to 0.25;
s is 0.001 to 0.1,
t is 0.001 to 0.1)
The heterogeneous material of embodiment 16 comprising:
(Embodiment 27)
Embodiment 27. The heterogeneous material of embodiment 26, wherein r is greater than 0.
(Embodiment 28)
27. The heterogeneous material of embodiment 26, wherein r is 0 and the semiconductor comprises a rutile phase and an anatase phase.
(Embodiment 29)
Embodiment 17. The heterogeneous material of embodiment 16, wherein the n-type semiconductor is tin oxide.
(Embodiment 30)
30. A method of degrading a compound comprising exposing the compound to a photocatalyst comprising a homogeneous material of any of embodiments 1-29 in the presence of light.
(Embodiment 31)
Embodiment 31. The method of embodiment 30 wherein the compound is a contaminant.
(Embodiment 32)
A method of killing a microorganism comprising exposing the microorganism to a photocatalyst comprising the homogeneous material of any of embodiments 1-29 in the presence of light.

I. Synthesis Example 1 (a). Synthesis of n-type semiconductor (Ex-1)
Ti (CNO) ₂ : Sn (Ex-1): Tin (II) 2-ethylhexanoate [also known as stannous octoate and / or stannous octoate] (Spectrum Chemicals, Gardena, CA) USA) 3.78 g, 50 wt% bis (ammonium lactato) titanium dihydroxide (IV) solution (titanium lactate, [Tyzor LA]) (Sigma Aldrich, St. Louis, MO, USA) 30 ml, and ammonium nitrate ( NH ₄ NO ₃ ) (Sigma Aldrich, St. Louis, MO, USA) 15.0 g 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 at 350 ° C. for 40 minutes in a preheated muffle furnace under ambient (room) atmosphere and pressure conditions. The resulting powder was placed in a preheated muffle furnace and then annealed at 475 ° C. for 40 minutes under ambient conditions.

Example 1 (b). Input Combustion synthesized Ti (O, C, N) ₂ : Sn (6 g) was mixed with 6M HCl (60 mL) at 90 ° C. for 3 hours with stirring in a water bath. The mixture was then cooled to room temperature, filtered through a 0.2 micron membrane filter paper, washed with 100-150 mL of deionized water (DI) water, and finally dried at room temperature overnight for 10-15 hours. .

The weight fraction of copper relative to the processed Ti (O, C, N) ₂ : Sn (1 g) was 0.01. A 10 mL aqueous solution of CuCl ₂ .2H ₂ O (26.8 mg) was stirred at 90 ° C. for 1 hour with 1 g of processed Ti (O, C, N) ₂ : Sn. Then 1.5 ml of an aqueous solution containing NaOH (50 mg) and glucose (250 mg) was added to the reaction mixture at 90 ° C. with 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 membrane, washed with 100 to 150 mL DI water, and finally Dry at 110 ° C. overnight (10-15 hours) in an air oven.

The weight ratio of CuO: Cu ₂ O in Ex-1 was determined to be 0.789: 0.211. By comparison, the CuxO / TiO ₂ nanocomposite obtained by the procedure of Qui et al., ACS Nano, 6, 1609-1618, had a CuO: Cu ₂ O weight ratio of 0.169: 0.831. It was.

Example 1 (b) '. Comparative Example 0 (CE-0)
The total weight percent of Cu as 0.25 wt% CuO + 0.125 wt% Cu ₂ O is physically added to the Sn—Ti (OCN) ₂ photocatalyst and physical using a mortar and pestle in 5-10 mL amounts of methanol. Mixed. Mixing was continued until all the methanol had evaporated.

Example 1 (c). Comparative Example 1 (CE-1)
_{CE-1 (Ti (CNO)} 2: Sn) is without introduction of Cu _x O (Step A only) Non-on type Ti _(CNO) 2: except that to obtain a Sn (without Cu _x O), Prepared in a similar manner to Example 1 (a).

Example 1 (d). Comparative Example 2 (Ex-1A)
Ex-1A was prepared in a similar manner as in Example 1 (b) above, except that 25 mg was used instead of 50 mg NaOH and 125 mg was used instead of 250 mg glucose.

Example 1 (d) '. Comparative Example 2 ′ (Ex-1B)
Ex-1B is a method similar to that in Example 1 (b) except that the weight fraction of copper with respect to the processed Ti (O, C, N) ₂ : Sn (1 g) is 0.005. It was prepared with.

Example 1 (e). Comparative Example 3 (Ex-2 and Ex-3)
Ex-2 (plasma WO ₃ ) and Ex-3 (commercial GTP WO ₃ ) use the same molar amount of plasma WO ₃ or commercial GTP-WO ₃ instead of Ti (O, C, N) ₂ : Sn photocatalyst And prepared in a similar manner to Ex-1 above, except that no NaOH was added to the reaction mixture and the amount of glucose was 125 mg instead of 250 mg. Plasma WO ₃ was made in a manner similar to that described in US patent application Ser. No. 13 / 738,243, filed Jan. 10, 2013, the teachings of which are incorporated herein by reference. . GTP WO ₃ was purchased from Global Tungsten & Powder (Towanda, PA, USA) and used without further purification or annealing.

0.159 mL of 1 mol solution of bis (ethylenediamine) copper (II) hydroxide was mixed with 10 mL of RO water and stirred at 90 ° C. for 1 hour with 1 g of WO ₃ . Glucose (125 mg) was then added to the reaction mixture at 90 ° C. with stirring. After the aqueous solution of glucose was added, the mixture was stirred for an additional hour, then cooled to room temperature, then filtered through a 0.2 micron membrane, washed with 100-150 mL DI water, and finally air oven And dried at 110 ° C. overnight (10 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 are in the case of Ex-1, except that the same molar amount of CeO ₂ is used instead of Ti (O, C, N) ₂ : Sn. Prepared in a similar manner. In addition, the input conditions were modified as follows: Ex-4: NaOH (25 mg) and glucose (125 mg) in water; Ex-5: No glucose; Ex-6: Glucose (62.5 mg) and NaOH (25 mg). concentration.

CE-2 is a non-input molar amount of CeO ₂ (Sigma Aldrich, St. Louis, MO, USA) with respect to CE-2 (relative to Ti (O, C, N) ₂ : Sn). Is similar to CE-1. CeO ₂ was used as received from the vendor without further purification or annealing.

Example 1 (g). Comparative Example 5 (Ex-7, CE-3)
Ex-7, except that Ti (O, C, N) ₂ : Sn is replaced by the same molar amount of insulator, Al ₂ O ₃ , NaOH 25 mg is used, and glucose 125 mg is used. Prepared in a similar manner to Ex-1. The input of Cu _x O was 1% by weight of Cu with respect to Al ₂ O ₃ . CE-3 is similar to CE-1 except that CE- ₃ is an equivalent non-input molar amount of Al ₂ O ₃ (relative to Ti (O, C, N) ₂ : Sn). . Al ₂ O ₃ was used as received from the vendor without further purification or annealing.

Example 1 (h). Comparative Example 6 (Ex-8, CE-4)
Ex-8 uses the same molar amount of n-type UV active photocatalyst, Ta ₂ O ₅ instead of Ti (O, C, N) ₂ : Sn, except that 25 mg NaOH and 125 mg glucose are used. Prepared in a similar manner to -1. The input of Cu _x O was 1% by weight of Cu with respect to Ta ₂ O ₅ . CE-4 is a non-input molar amount of Ta ₂ O ₅ (Sigma Aldrich, St. Louis, MO, USA) with CE-4 (relative to Ti (O, C, N) ₂ : Sn). Except that it is similar to CE-1. Ta ₂ O ₅ was used as received from the vendor without further purification or annealing.

Example 1 (i). Comparative Example 7 (Ex-9, Ex-10, Ex-11, Ex-19, Ex-20, CE-4A)
Ex-9 _{are, Ti (O, C, N} ) 2: the same amount of n-type UV active photocatalyst instead of Sn, but using SnO _2, was prepared in a manner similar to the case of the ex-1. The input of Cu _x O was 1% by weight of Cu with respect to SnO ₂ . Nano-sized SnO ₂ (US Research Nanomaterial, Houston, TX, USA) was annealed at 900 ° C. for 1 hour in air in a box furnace. Subsequently, it was immersed in 6M HCl aqueous solution like Ex-1. In 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, annealed SnO ₂ was not immersed in 6M HCl aqueous solution like 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 was 25 mg and the amount of glucose was 10 mg. CE-4A is similar to CE-1 except that CE-4A is an equivalent non-input molar amount of SnO2 (relative to Ti (O, C, N) ₂ : Sn). By varying the amount of NaOH and glucose while introducing 1 wt% of Cu a fixed amount relative to the SnO _2, the body color of the different appearance is obtained.

Example 1 (j). Comparative Example 8 (Ex-12, CE-5, Ex-13)
Ex-12 was prepared in a similar manner to Ex-1B above. Cu _x O was charged to rutile TiO ₂ (Taika, Osaka, Japan) except that 25 mg was used instead of 50 mg NaOH and 125 mg was used instead of 250 mg glucose.

CE-5 is CE-5 (except for Ti (O, C, N) ₂ : Sn) with an equivalent non-input molar amount of rutile TiO 2 (Taika, Osaka, Japan), Similar to CE-1. Rutile TiO2 was used as received from the vendor without further purification or annealing.

In Ex-13, 10 g of commercial WO ₃ (Global Tungsten Powder, Sylvania, PA, USA) was annealed at 400 ° C. for 1 hour. [Pt (NH ₃ ) ₄ ] Cl ₂ (0.181 mg Alfa Aesar, Ward Hill, MA, USA)] was dissolved in 15.0 mL RO water and at room temperature (RT) with 2.0 g annealed WO _3. Stir for 2 hours. It was then filtered through a 0.2 micron membrane filter paper, washed with RO water and dried at 120 ° C. overnight. The resulting material was annealed in air at 400 ° C. for an additional hour.

Example 1 (k). Comparative Example 9 (Ex-13 to 17, CE-6)
Ex-14 to Ex-17 were prepared in a manner similar to that described above, except that different amounts of [Pt (NH ₃ ) ₄ ] Cl ₂ ] and / or IrCl ₃ / IrO ₂ were dissolved in 15 mL of RO water. did. See Table 1 below:

CE-6 is CE except that CE-5 is WO ₃ (Global Tungsten Powder, PA, USA) with an equivalent non-input molar amount (relative to Ti (O, C, N) ₂ : Sn). Similar to -1. WO ₃ was used as received from the vendor without further purification or annealing.

Example 1 (l). Synthesis of n-type semiconductor (Ex-18)
Synthesis of MgTi2O5: Mg (NO ₃ ) ₂ · 6H ₂ O (Sigma Aldrich, St. Louis, MO, USA) 2.663 g, ammonium nitrate (Sigma Aldrich, St. Louis, MO, USA) 5 g, urea (Sigma Aldrich, St. Louis, MO, USA) 1.5 g, and 10 mL of bis (ammonium lactate) titanium hydroxide (IV) (titanium lactate, [Tyzor LA]) (Sigma Aldrich, St. Louis, MO, USA) Dissolved in about 10 mL of DI water in a low format Pyrex® beaker. The resulting mixture was then heated at 350 ° C. for 20 minutes in a preheated muffle furnace under ambient (room) atmosphere and pressure conditions. The resulting powder was placed in a preheated muffle furnace and then annealed at 600 ° C. for about 30 minutes under ambient conditions.
Cu _x O MgTi is turned ₂ O _5: Cu _x O, except not using the HCl preparation step in this preparation, poured into MgTi ₂ O ₅ in a manner similar to that described in Example 1 (b) did. The NaOH preparation step used was similar to that described in Example 1 (b). The weight fraction of copper with respect to MgTi ₂ O ₅ was 0.01. 10 mL of an aqueous solution of CuCl ₂ .2H ₂ O (26.8 mg) was stirred at about 90 ° C. for about 1 hour with 1 g of MgTi ₂ O ₅ . Then 1.5 mL of an aqueous solution containing NaOH (25 mg) and glucose (125 mg) was added to the reaction mixture at about 90 ° C. with stirring. After addition of an aqueous solution of glucose and NaOH, the mixture was stirred for about an additional hour, then cooled to room temperature, then filtered through a 0.05 micron membrane, washed with 100 to 150 mL DI water, and finally And dried in an air oven at 110 ° C. for about 2 hours.
Example 1 (m). (Ex-20 (multi-phase TiO _{2 with} Cu _x O added))
A multi-phase n-type semiconductor was put into CuxO by a method similar to that in Example 1 (b). N-type semiconductor of a plurality of phases (TiO2 87% of anatase phase / _TiO 2 13% of the rutile phase, trade name "P25" [EvoniK Degussa, NJ, USA] for sale) weight fraction of copper to the 0 .01. 15 mL of an aqueous solution of CuCl ₂ .2H ₂ O (26.8 mg) was stirred at about 90 ° C. for 1 hour with 1 g of P25. Then 1.5 mL of an aqueous solution containing NaOH (25 mg) and glucose (125 mg) was added to the reaction mixture at about 90 ° C. with stirring. After addition of an aqueous solution of glucose and NaOH, the mixture was stirred for about an additional hour, then cooled to room temperature, then filtered through a 0.05 micron membrane, washed with 100 to 150 mL DI water, and finally And dried in an air oven at 110 ° C. for about 2 hours.

Example 1 (n) (CE-7)
Comparative Example CE-7 was prepared by adding 0.25 wt% CuO + 0.125 wt% Cu 2 O, 0.625 wt% P25 to methanol (5-10 mL), and until this methanol was substantially all evaporated. It was prepared in a manner similar to Example 1 (m) except that it was physically mixed by hand.

Example 1 (o). _{(Ex-19 (AgVWO 6)} )
Vanadyl oxalate (Stratacor, Inc, Arkansas, USA) 4.12 g, Glycine (Sigma Aldrich, St. Louis, MO, USA) 0.3 g, Ammonium nitrate (Sigma Aldrich, St. Louis, MO, USA) 0.62 g, And 1.484 g of ammonium metatungstate (Global Tungsten & Powder, PA, USA) were dissolved in about 5 mL of reverse osmosis (RO) purified water. To this solution, 1 g of silver nitrate (Alfa Aesar, USA) was added to give a brown slurry in a 250 mL low format beaker and then the resulting mixture was then preheated under ambient (room) atmosphere and pressure conditions. Heated at about 350 ° C. for about 20 minutes in a muffle furnace. The resulting powder was placed in a preheated muffle furnace and then annealed at about 500 ° C. for about 60 minutes under ambient conditions, resulting in a yellow powder (Ex-19).

Example 1 (p). _{(Ex-20 (AgCa 2 Zn} 2 V 3 O 12))
Vanadyl oxalate (Stratacor, Inc, Arkansas, USA) 6.19 g, Glycine (Sigma Aldrich, St. Louis, MO, USA) 1.11 g, Zinc nitrate hexahydrate (Sigma Aldrich, St. Louis, MO, USA) ) 1.75 g, calcium nitrate tetrahydrate (Sigma Aldrich, St. Louis, MO, USA) 1.39 g, ammonium nitrate (Sigma Aldrich, St. Louis, MO, USA) 2.49 g, reverse osmosis (RO) Dissolved in about 10 mL of purified water. To this solution, 0.5105 g of silver nitrate (Alfa Aesar, USA) was added to give a brown slurry in a 250 mL low format glass beaker, then the resulting mixture was then mixed with ambient (room) atmosphere and pressure conditions. Then, it was heated at about 350 ° C. for about 20 minutes in a preheated muffle furnace. The resulting powder was placed in a preheated muffle furnace and then annealed at about 600 ° C. for about 60 minutes under ambient conditions, resulting in a yellow powder (Ex-20).

Example 1 (q). (Ex-21 (Ag ₃ PO ₄ ))
5 g of silver nitrate (Alfa Aesar, USA) was dissolved in 10 mL of reverse osmosis (RO) purified water in a 50 mL glass beaker. In a separate 50 mL glass beaker, 1.128 g ammonium dihydrogen phosphate (Sigma Aldrich, St. Louis, MO, USA) was dissolved in 10 mL reverse osmosis (RO) purified water. An aqueous silver nitrate solution was added dropwise to an aqueous solution of ammonium dihydrogen phosphate while stirring the ammonium dihydrogen phosphate solution. The yellow precipitate formed during this addition at room temperature was finally filtered and dried in an air oven at 110 ° C. for 2 hours.

Example 2: Characterization of supported P catalyst Example 2 (a): Powder XRD characterization (Ex-1A, CE-1, Ex-4, CE-2, Ex-7, and CE-3)
Ex-1A, CE-1, Ex-4, CE-2, Ex-7, and CE-3 powder samples were analyzed by powder x-ray diffraction (Rigaku Miniflex II [Rigaku Americas, Woodland) using Cu K-α radiation. , TX, USA) at 1 ° / min. The results of X-ray diffraction analysis of Ex-1 and CE-1 are shown in FIG. 3, confirming the presence of anatase TiO ₂ . From the XRD pattern (FIG. 3), it was confirmed that the anatase phase of Ti (O, C, N) 2: Sn was retained even after the introduction of Cu _x O. The reason was obtained. Comparison of XRD spectrographs with the Joint Committee for Powder Diffraction Standards by International Diffraction Data Center (Newton Square, PA, USA), card number 00-021-1272 [anatase-TiO2] (JCPDS) This is because it shows substantially the same peak as the phase spectrogram (the phase of the material is generally active by photocatalysis for visible light).

Furthermore, Ex-4 and Ex-7 powder samples were analyzed in a manner similar to Ex-1A above, except that equimolar amounts of Ex-4 and Ex7 were used instead of Ex-1A. The results are shown in FIGS. 4 and 5, each using powder x-ray diffraction (Rigaku Miniflex II [Rigaku Americas, Woodland, TX, USA) using Cu K-α radiation at 1 ° / min. The X-ray diffraction results shown in FIGS. 4 and 5 confirm that the Cu _x O input has not substantially affected the bulk semiconductor phase of the respective n-type material.

Example 2 (b): DRS characterization Ex-1A, CE-1 (FIG. 6); Ex-4, and CE-2 (FIG. 7), Ex-7, and CE-3 (FIG. 8) powders Samples were analyzed using diffuse reflectance spectroscopy (DRS). The results are shown in FIGS. 6, 7, and 8, at least tin doping (Ex-1), CeO ₂ (Ex-4), and Al ₂ O ₃ (Ex-7) in the visible spectrum (400 nm to 800 nm). It has been shown that CE-1, CE-2, and CE-3 did not appear to improve, whereas it appeared to improve the absorption of. Therefore, the anatase TiO2 observed in the XRD pattern and visible absorption confirms that Ti (O, C, N) ₂ : Sn, CeO ₂ , and Al ₂ O ₃ are input to the substrate due to the anatase phase. It was. The input Cu _x O has absorption on the longer wavelength side of the absorption edge of the semiconductor, and when the input Cu _x O has a mixture of CuO and Cu ₂ O, the input In addition to the absorbed Cu _x O, their characteristic absorptions between 600 and 800 nm and between 500 and 600 nm are observed, respectively.

Example 3 Experimental preparation for photocatalysts (Ex-1A and CE-1)
Ex-1A (130 mg) prepared by the method described earlier in this disclosure was added to 1.04 ml of DI water to make a coating solution with 10 wt% solid material added to water. The resulting dispersion was homogenized using an ultrasonic homogenizer. A glass substrate (50 mm × 75 mm) was coated with what was prepared by using a spin coater (1200 rpm / 40 seconds). The coated substrate was heated at 120 ° C. for 2 minutes. Another slide was made in the same manner except that CE-1 (130 mg) was used instead of Ex-1A.

The spin-coated slide glass was heated at 120 ° C. on a hot plate under full spectrum irradiation for 1 hour with a Xe (xenon) lamp (lamp power output 300 W). Each slide was then sealed in a separate 5 L Tedlar bag under vacuum, after which 3 L of ambient air and 80 mL of 3500 ppm acetaldehyde were injected. Each bag was lightly rubbed 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 gas chromatography-hydrogen ionization detector (GC-FID). Each Tedlar bag containing the sample was placed in the original dark for 1 hour. The slide / Tedlar bag was exposed to a 455 nm array blue LED with a light intensity of 270 mW / cm ² . Samples were collected every 30 minutes by GC-FID autoinjection port and the amount of remaining acetaldehyde was evaluated at subsequent 30 minute intervals. FIG. 9 is a graph showing VOC performance data of Ex-1A. The graph generally shows that when Ti (CNO) ₂ : Sn is combined with Cu _x O (Ex-1A), performance is improved when compared to bare Ti (CNO) ₂ : Sn (CE-1). Indicates.

Example 4 Antibacterial experiment.
Example 4A.
A substrate (1 ″ × 2 ″ slide glass) was made by sequentially applying 70% IPA (isopropyl alcohol) and 100% ethanol (EtOH) and then drying in air. Ex-1B was dispersed in 100% EtOH at a concentration of 2 mg / mL, then 100 uL of the suspension was applied to the substrate and then dried. The coating process was repeated 5 times to obtain 1 mg of Ex-1B on the substrate. The substrate was then dried at room temperature. The coated substrate was placed in a glass dish with filter paper soaked in water to maintain moisture, and a glass spacer was inserted between the substrate and the filter paper to separate them.

E. E. coli (ATCC 8739) was streaked onto a 10 cm diameter Petri dish containing 20 mL of LB (lysogenic broth / Luria broth) agar and incubated overnight at 37 ° C. For each experiment, a single colony was picked and inoculated with 3 mL of nutrient broth and the inoculated culture was incubated at 37 ° C. for 16 hours to produce an overnight culture (approximately 109 cells / mL). For fresh logarithmic growth phase culture of overnight culture, dilute the overnight culture to x100, inoculate into another 5 cm Petri dish containing LB agar and incubate at 37 ° C. for 2.5 hours. Was obtained by The fresh culture was diluted 50 × with 0.85% saline, which gave a cell suspension of 2 × 10 ⁶ cells / mL. 50 μL of the cell suspension was pipetted onto each deposited glass substrate. A sterile (70% then 100% EtOH) plastic film (20 mm x 40 mm) was placed on the suspension and spread evenly under the film. Was irradiated with - (dark _Cu x _{O 2),} or followed by a blue LED light (455 nm, 10 mW / cm @ 2) holding the specimen in the dark (CuO ₂ - bright). At selected time points, eg, every 30/60 minutes, the specimens were placed in 10 mL of 0.85% saline and swirled to wash away the bacteria. The washed-out suspension is retained and then serially diluted using 0.85% saline, then plated on LB agar and incubated overnight at 37 ° C. to determine the number of viable cells as CFU / specimen Were determined.

  The results are shown in FIGS. Due to the presence of flexible copper ions. E. coli killing properties appear to have been observed within 30 minutes even in the dark (see FIGS. 10 and 11).

FIG. Also shown is the characteristics of Cu ¹⁺ after being injected into CeO ₂ , where complete killing of E. coli is observed in the dark for 1 hour as well as under a blue LED of 10 mW / cm 2 455 nm light. Therefore, CeO ₂ into which Cu _x O is added is E.I. It is a functional material that is good at killing E. coli.

Example 4B
Ex-1 powder was prepared as described in Example 1. The powder was then kept in the dark at 85% relative humidity and 85 ° C. for a period of 7 days. Slides were then prepared and tested for antimicrobial activity in the same manner as described in Example 4A. The results are shown in FIG. 12A. The results show that Ex-1 demonstrated retained photocatalytic activity even after exposure to 85% relative humidity and 85 ° C. for a period of 7 days.

Example 4C
Ex-7 powder was prepared as described above. The powder was then held at 300 ° C. for 20 minutes in the dark. Slides were then prepared and tested for antimicrobial activity in the same manner as described in Example 4A. The result is shown in FIG. 12B. The results show that Ex-7 retained photocatalytic activity even after exposure at 300 ° C. for 20 minutes.

５Ｂ
Ｅｘ−１８（Ｃｕ_ｘＯが投入されたＭｇＴｉ２Ｏ５）に関する光触媒特性は、天然青色粉末として食品添加物色素（Ｎａｔｕｒａｌ Ｂｌｕｅ Ｃｏｌｏｒｅｄ ｐｏｗｄｅｒ、Ｃｏｌｏｒ Ｍａｋｅｒ、Ａｎａｈｅｉｍ、Ｃａｌｉｆｏｒｎｉａ、ＵＳＡ）の分解を測定することによって検査した。分解は、実施例５Ａに記述された手法で検査した。結果を図１７に示す。 Example 5 FIG. Photocatalytic experiments for dye discoloration studies Example 5A.
The photocatalytic properties of Ex-1, CE-1, and rutile TiO2 with and without Cu _x O were dissolved in 2.85 g of natural blue powder dissolved in 100 mL of RO water. Comparisons were made by measuring the degradation of food additive dyes (Natural Blue Colored powder, Color Maker, Anaheim, California, USA) when producing stock solutions. 150 mg of each sample was placed in RO water (27 mL) containing 3 mL of natural blue blue powder solution for 1 hour without any light and then exposed to a blue light emitting diode (455 nm, 45 mW / cm ² ) for 5 hours. . The degradation of the resulting blue solution was monitored by UV-Vis absorption spectroscopy (Cary-50, Spectrophotometer Agilent Technologies, Santa Clara, CA, USA) for 1 hour, 3 hours, and Measured at 5 hours. The concentration was calculated as the peak intensity at 600 nm. The results are shown in FIG. Table 2 below compares the final degradation results for the four photocatalytic materials.

5B
The photocatalytic properties for Ex-18 (MgTi2O5 with Cu _x O input) were examined by measuring the degradation of food additive dye (Natural Blue Colored powder, Color Maker, Anaheim, California, USA) as a natural blue powder. . Degradation was examined by the technique described in Example 5A. The results are shown in FIG.

Photocatalytic experiment for antibacterial studies Example 6A.
130 mg of each powdered sample (Examples 14-18 above) was dissolved in a minimum amount of RO water (about 15 mL) and homogenized for 5 minutes.

A clean petri dish was wiped with ethanol and the inner surface of the dish was ionized with a plasma device for 1-2 minutes. A homogeneous sample of each compound was poured into a treated petri dish and then heated at 120 ° C. with agitation to increase its uniform distribution as the sample dried. After the sample dried, the Petri dish was placed under a UV lamp (300 W) for 1 hour. Each Petri dish was then sealed in a separate 5 L Tedlar bag in vacuum, after which 3 L of ambient air and 80 mL of 3500 ppm acetaldehyde were injected. Each bag was lightly rubbed 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 gas chromatography-hydrogen ionization detector (GC-FID). Each Tedlar bag containing the sample was placed in the original dark for 1 hour. The slide / Tedlar bag was exposed to a 455 nm array blue LED with a light intensity of 0.656 mW / cm ² . Samples were collected every 30 minutes by GC-FID autoinjection port and the amount of remaining acetaldehyde was evaluated at subsequent 30 minute intervals. The results are shown in Table 3 below.

FIG. 14 shows WO ₃ (commercial GTP) (CE-6), WO ₃ (Ex-13) charged with 0.05 mol% of Pt, and WO ₃ (Ex−) charged with 0.1 mol% of IrO _2. 16) shows the decomposition rate (Ct / Co) of acetylaldehyde by WO ₃ (twice) (Ex-17) in which 0.05 mol% of Pt and 0.1 mol% of IrO 2 were added together. Observing the results that under the 455 nm (0.656 mW / cm ² ) blue LED, the introduction of Pt had a good effect and WO ₃ into which only IrO ₂ was introduced has no effect on the decomposition of acetaldehyde. Interesting. However, when both Pt (0.05 mol%) and IrO ₂ (0.1 mol%) are introduced into WO ₃ , only Pt (0.05 mol%) or only IrO ₂ (0.1 mol%) or bare GTP When compared to the case of WO ₃ alone, it resulted in a further enhancement of acetaldehyde photolysis under the same conditions.

Example 5c
Ex-10 (SnO ₂ ), CE-4A, and food additive dye FD & C Blue No. The photocatalytic properties relating to only two dyes were compared with the food additive dye FD & C Blue No. Comparison was made by measuring the degradation of the two dyes (synthetic blue powder, Chromatech, Inc, Michigan, USA). G of natural blue powder was dissolved in 100 mL of RO water to produce a blue powder stock solution. 150 mg of each sample was added. Photocatalytic properties were determined by the procedure described in Example 5a. The results are shown in FIG.

The photocatalytic properties for Ex-18 (MgTiO ₅ ) and Ex-1 (SnTi (OCN) ₂ ) loaded with Cu _x O were compared with the food additive dye FD & C Blue No. Comparison was made by measuring the degradation of the two dyes (synthetic blue powder, Chromatech, Inc, Michigan, USA). 2.85 g of natural blue powder was dissolved in 100 mL of RO water to produce a blue powder stock solution. 150 mg of each sample was added. Photocatalytic properties were determined by the procedure described in Example 5a. The results are shown in FIG.

Example 6 E. coli (ATCC 8739) photocatalytic deactivation 6A Method:
A substrate (1 "x 2" slide glass) was made by successively applying 70% IPA (isopropyl alcohol) and 100% ethanol (EtOH) and then drying in air. Ex-1B was dispersed in 100% EtOH at a concentration of 2 mg / mL, then about 100 uL of the suspension was applied to the substrate and then dried. The coating process was repeated 5 times to obtain about 1 mg of Ex-1B on the substrate. The substrate was then dried at room temperature. The coated substrate was placed in a glass dish with filter paper soaked in water to maintain moisture. A glass spacer was inserted between the substrate and the filter paper to separate the substrate from the filter paper.

E. E. coli (ATCC 8739) was streaked onto a 5 cm diameter petri dish containing about 25 ml of LB agar and incubated overnight at about 37 ° C. For each experiment, a single colony was picked and inoculated with about 3 mL of nutrient broth, and the inoculated culture was incubated at about 37 ° C. for about 16 hours to produce an overnight culture (about 10 ⁹ cells / mL). A fresh logarithmic growth phase culture of the overnight culture is prepared by diluting the overnight culture to x100, inoculating into another 5 cm Petri dish containing LB agar and then at about 37 ° C. at about 2.5. Obtained by incubating for hours. The fresh culture was diluted 50 ×, which gave a cell suspension of approximately 2 × 10 ⁶ cells / mL. 50 uL of cell suspension was pipetted onto each glass substrate. A sterile (70% then 100% EtOH) plastic film (20 mm x 40 mm) was placed over the suspension to spread the suspension evenly under the film. At selected time points, for example every 30 minutes, the specimens were placed in 10 mL of 0.85% saline and swirled at 3200 rpm for about 1 minute to wash off the bacteria. The washed-out suspension was serially diluted using 0.85% saline, plated on LB agar and incubated overnight at about 37 ° C. to determine the number of viable cells as CFU / specimen. Counts were made by visual inspection and the results were multiplied by a dilution factor to reach the determined number. The specimen was then irradiated with a 455 nm blue light emitting LED and positioned underneath to provide the specimen with about 45 mw / cm ² . The results are shown in FIG.

  The antimicrobial properties of CE-7 and Ex-7A were determined as described in Example 6A, except that the molar equivalents of CE-7 and Ex-7A were used instead of Ex-1B. The results are shown in FIGS. 17 (CE-7) and 18 (Ex-7A).

Ex-1 (with 1% Cu _x O / Sn: Ti (OCN) ₂ input), Cu _x O alone, and non-input Sn: Ti (OCN) ₂ (described in Example 1 (a)) Antimicrobial properties) were compared by measuring antimicrobial activity as described in Example 6A. The results are shown in FIG.

Function of Photocatalyst I 1 mg of 10% bleach (Clorox Germincidal, NaClO system) in 50 ml of Cu _x O / P25 (as produced in Example 1 (m)) in a 1.6 ml Eppendorf centrifuge tube and Mix and incubate for 2 hours at room temperature (about 24 ° C.) with shaking (set on analog VWR vortex 9). After incubation, the tube was centrifuged with an Eppendorf 5430 microcentrifuge (14167 rcf for 2 minutes), after which the particles formed a solid pellet at the bottom of the tube. The clear supernatant was carefully removed and 1 mL of DI water was added. The tube was swirled until the pellet was completely broken up and the suspension was homogeneous. It was then centrifuged again. This process was repeated four more times.

  After final centrifugation, the pellet was resuspended in 1 mL DI water and mixed with 4 mL DI water in a 20 mL clear glass vial with a lid. 5 mL of methanol was added to bring the total volume in the vial to approximately 10 mL.

  A magnetic stir bar (1/2 "x 1/8", disposable) was added to the vial and placed on a stir plate (1000 rpm). A 300 W xenon lamp (Oriel 68811) was placed approximately 15 cm away from the vial wall. Irradiation continued for 1 hour in the exhaust hood and during this process there was a negligible temperature change in the vial.

  After irradiation, the contents of the vial were centrifuged to remove all liquid. The pellet was vacuum dried and resuspended in 25 mL of 200 proof ethyl alcohol. The mixture was then sonicated with a sonicator for 20 minutes.

  100 microliters of the sonicated dispersion was spread evenly on one side of a 1 "x 2" slide glass. After the surface was dry (in the exhaust hood), the process was repeated for a total of 5 coatings. The coated slide was then used in our standard bacterial test.

For control purposes, 50 mg of Cu _x O / Al ₂ O ₃ was treated in the same manner as above and then used to make a coated slide. These control slides were subjected to standard bacterial testing in the same manner as Cu _x O / P25. The dark test results were plotted.

As shown in FIG. 22 (left), fresh Cu _x O / P25 (1) showed high activity and E. coli. E. coli was reduced by 3 log units in 30 minutes in the dark. Bleached material (2) showed a significant reduction in activity, achieving only a 3 log reduction after 2 hours in the dark. After the bleaching treatment, the material was irradiated with a xenon lamp, but the resulting sample (3) showed activity comparable to the untreated sample (1), again achieving a 3 log reduction in 30 minutes.

In contrast, such functional recovery by irradiation was not seen in the case of Cu _x O / Al ₂ O ₃ (FIG. 22, right), but it was bleached / irradiated sample (3 ) Was similar to that of the only bleached sample (2) but showed significantly less activity than the fresh sample (1).

Photocatalyst II function In order to investigate how the duration of the bleaching treatment affects the activity of the material charged with copper oxide, the above experiment was performed with the bleaching treatment duration set at 2 and 16 hours. Carried out. All other aspects of the experiment remained the same. The log reduction results from these treated samples were plotted along with the results from untreated material.

In FIG. 23 and the left figure, the bleaching treatment of Cu _x O / Al ₂ O ₃ resulted in a significant decrease in dark place activity. Testing under light failed to restore activity to any broad extent. In contrast, in the case of the Cu _x O / P catalyst (P25) (FIG. 23, right), the dark place activity was similarly affected, but the activity in the bright place was restored. The important point of this experiment is that even after 16 hours of bleaching treatment, the recovery process in bright places remained largely intact, with respect to the durability of Cu _x O / P25. Showed strong evidence.

Aqueous combustion synthesis of WO ₃ doped with boron:
A boron doped WO ₃ with ε phase was prepared using an aqueous combustion method.

Ammonium metatungstate hydrate (Inframat Advanced Materials, Manchester, CT, USA) 5 gm, boric acid (Sigma-Aldrich, St. Louis MO, USA) 100 mg, carbohydrazide (Sigma-Aldrich) Si, and ammonium nitrate (Sigma-Aldrich) Si Aldrich) 10 g was dissolved in 50 ml DI water. The aqueous solution was then placed in a muffle furnace and preheated to about 420 ° C. until combustion was substantially complete (about 20 minutes). After combustion was complete, the product was annealed in air at about 425 ° C. for about 30 minutes. The powder body color appeared orange-yellow, which was confirmed by comparison of the powder XRD pattern (FIG. 1) and standard εWO ₃ x-ray diffraction (ICFF PDF card number 01-087-2404).

  Figure 1: Powder XRD pattern (right).

Surface modification of εWO3 by a powerful and selective absorption method using cobalt oxide:
1 gm of εWO ₃ and 40.37 g of CoCl ₂ .4H ₂ O were dissolved in about 10 mL of DI water and stirred in a 40 mL closed vial reactor at about 90 ° C. for about 2 hours. The closed vial reactor is then quenched with tap water, filtered through a membrane filter [miniaturized to 0.05 microns], washed several times with DI water (at least about 250 ml), and finally about 110 ° C. And dried for about 2 hours to obtain εWO ₃ charged with cobalt oxide.

  Unless otherwise indicated, all numerical values representing the amounts of ingredients used in the specification and claims, properties such as molecular weight, reaction conditions, etc. are modified in all cases by the term “about”. Please understand that. Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and the appended claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not intended to limit the application of the doctrine of equivalents of the claims, each numeric parameter is compared to the reported significant figures and by applying normal rounding techniques, At least it should be interpreted.

  The terms “a”, “an”, “the”, and similar designations used in the context of describing the present invention (particularly in the context of the following claims) are not specifically indicated herein. It should be construed to include both the singular and plural unless specifically stated otherwise by context or context. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples or exemplary languages (eg, “etc.”) provided herein are merely illustrative of the present invention and impose any claim limitations. It is not a thing. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

  Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be mentioned and may be recited in the claims individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of the group may be included or removed from the group for convenience and / or for patentability reasons. If any such inclusions or deletions are made, this specification shall be deemed to contain the modified group and thus satisfy the written description of all Markush groups used in the appended claims.

  Certain specific embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The present inventors expect that those skilled in the art will appropriately use such modifications, and the present inventors will implement the present invention by means other than those specifically described in this specification. Intended. Accordingly, the claims include all modifications and equivalents of the subject matter recited in the claims as permitted by applicable law. Moreover, any combination of all possible variations of the above-described elements is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context.

  Finally, it is to be understood that the embodiments disclosed herein are illustrative of the claimed principles. Other modifications that may be used are within the scope of the claims. Thus, by way of example and not limitation, alternative embodiments may be utilized in accordance with the teachings herein. Thus, the claims are not strictly limited to the embodiments as illustrated and described.

10 conduction band 20 valence band 25 overlap

Claims (32)

A p-type semiconductor comprising a first metal oxide compound and a second metal oxide compound, wherein the first metal oxide compound and the second metal oxide compound have different oxidation states of the same metal. A p-type semiconductor having a p-type valence band;
An inhomogeneous material comprising an n-type semiconductor having an n-type valence band deeper than the p-type valence band and communicating with the p-type semiconductor by ionic charges.   The heterogeneous material according to claim 1, further comprising a noble metal in communication with the first metal oxide compound and the second metal oxide compound by an ionic charge.   The heterogeneous material according to claim 2, wherein the noble metal is rhodium, ruthenium, palladium, silver, osmium, platinum, or gold.   The heterogeneous material according to claim 2, wherein the noble metal is introduced into 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 an ionic charge isolated from the p-type semiconductor.   The heterogeneous material according to claim 5, wherein the second n-type semiconductor comprises cerium oxide. The heterogeneous material of claim 6, wherein the cerium oxide is CeO ₂ . The heterogeneous material according to claim 5, wherein the second n-type semiconductor comprises multi-phase TiO ₂ .   The first metal oxide compound includes copper (I) and the second metal oxide compound includes copper (II), the first metal oxide compound includes cobalt (II) and the first The second metal oxide compound includes cobalt (III), the first metal oxide compound includes Mn (II), and the second metal oxide compound includes Mn (III), The metal oxide compound includes Fe (II) and the second metal oxide compound includes Fe (III), or the first metal oxide compound includes Ir (III) and the second metal The heterogeneous material of claim 1, wherein the oxide compound comprises Ir (IV).   The heterogeneous material according to claim 1, wherein the p-type semiconductor is introduced into the n-type semiconductor.   The heterogeneous material according to claim 1, wherein the p-type semiconductor is substantially uniformly dispersed on 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 size of 100 nm or less.   The heterogeneous material according to claim 9, wherein the p-type semiconductor comprises copper (I) and copper (II). The heterogeneous material of claim 13, wherein the p-type semiconductor comprises Cu _x O. The heterogeneous material of claim 14, wherein the Cu _x O is chemically valence controlled.   The heterogeneous material according to claim 9, wherein the ratio of copper (I): copper (II) is between 10:90 and 30:70.   The heterogeneous of claim 1, wherein the p-type semiconductor is 0.001 to 10% by weight of the heterogeneous material and the n-type semiconductor is 90 to 99.999% by weight of the heterogeneous material. material.   The heterogeneous material according to claim 1, wherein the n-type semiconductor is an oxide of cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, or aluminum. The n-type semiconductor is 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. The heterogeneous material of claim 1, comprising 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 (where 0 <x <2). The heterogeneous material according to claim 1, wherein the n-type semiconductor is Zr _1-y Ce _y TiO ₄ (where 0 <y <1).   The heterogeneous material according to claim 1, wherein the n-type semiconductor is titanium oxide having a valence band controlled through doping.   The heterogeneous material of claim 1, wherein the n-type semiconductor is titanium oxide doped with N, C, or both. The n-type semiconductor, wherein _{(Ti 1-r M r)} compounds represented by _{(O 2-s-t C} s N t) ( in the formula,
M is Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn, Cu, or combinations thereof;
r is from 0 to 0.25;
s is 0.001 to 0.1,
t is 0.001 to 0.1)
The heterogeneous material according to claim 1, wherein the heterogeneous material is titanium oxide. _{(Ti 0.99 Sn 0.01) (O} 2-s-t C s N t), (Ti 0.97 Sn 0.03) (O 2-s-t C s N t), (Ti 0. _{95 Sn 0.05) (O 2-} s-t C s N t), (Ti 0.90 Sn 0.10) (O 2-s-t C s N t), (Ti 0.85 Sn 0. _{15) (O 2-s-} t C s N t), (Ti 0.985 Ni 0.015) (O 2-s-t C s N t), (Ti 0.98 Ni 0.02) (O _{2-s-t C s N} t), (Ti 0.97 Ni 0.03) (O 2-s-t CsNt), (Ti 0.99 Sr 0.01) (O 2-s-t CsNt) _{, (Ti 0.97 Sr 0.03) (} O 2-s-t CsNt), (Ti 0.95 Sr 0.05) (O 2-s-t C s N t), ( _{i 0.97 Ba 0.03) (O 2} -s-t C s N t), (Ti 0.95 Ba 0.05) (O 2-s-t C s N t), (Ti 0.94 _{Sn 0.05 Fe 0.01) (O 2} -s-t C s N t), (Ti 0.94 Sn 0.05 Ni 0.01) (O 2-s-t C s N t), ( _{Ti 0.99 Fe 0.01) (O 2} -s-t C s N t), (Ti 0.95 Zn 0.05) (O 2-s-t C s N t), (Ti 0.77 _{sn 0.15 Cu 0.08) (O 2} -s-t C s N t), (Ti 0.85 Zn 0.15) (O 2-s-t C s N t), (Ti 0.90 _{Bi 0.10) (O 2-s} -t C s N t), (Ti 0.996 V 0.004) (O 2-s-t CsNt), (Ti 0.984 V 0. _{016) (O 2-s-} t C s N t), (Ti 0.970 V 0.03) (O 2-s-t C s N t), (Ti 0.997 Mo 0.003) (O _{2-s-t C s N} t), (Ti 0.984 Mo 0.016) (O 2-s-t C s N t), (Ti 0.957 Mo 0.043) (O 2-s- _{t C s N t), (} Ti 0.97 W 0.03) (O 2-s-t C s N t), (Ti 0.95 W 0.05) (O 2-s-t C s N _{t), (Ti 0.996 V 0.004} ) (O 2-s-t C s N t), (Ti 0.984 V 0.016) (O 2-s-t C s N t), or (Ti _0.970 V _0.03 ) (O _2−s−t C _s N _t )
25. The heterogeneous material of claim 24, comprising: The n-type _{semiconductor, (Ti 1-r M r} ) (O 2-s-t C s N t)
(Where
M is Sn,
r is from 0 to 0.25;
s is 0.001 to 0.1,
t is 0.001 to 0.1)
The heterogeneous material of claim 16 comprising:   27. The heterogeneous material of claim 26, wherein r is greater than zero.   27. The heterogeneous material according to 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 tin oxide.   A method for decomposing a compound comprising exposing the compound to a photocatalyst comprising the homogeneous material of claim 1 in the presence of light.   32. The method of claim 30, wherein the compound is a contaminant.   A method for killing microorganisms comprising the step of exposing the microorganisms to a photocatalyst comprising the homogeneous material of claim 1 in the presence of light.

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