CN105163847B

CN105163847B - Multivalence photocatalysis heterogeneous material for semiconductor

Info

Publication number: CN105163847B
Application number: CN201480017897.7A
Authority: CN
Inventors: 伊坎巴拉姆·山姆班登; 张彬
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2013-03-15
Filing date: 2014-03-13
Publication date: 2018-04-03
Anticipated expiration: 2034-03-13
Also published as: EP2969186A1; WO2014151861A1; CN105163847A; JP6462658B2; JP2016512164A; TWI633932B; TW201500112A

Abstract

This document describes heterogeneous material, and it is included：P-type semiconductor, it includes two kinds of metal-oxide compounds of the same metal in two kinds of different oxidation state；And n-type semiconductor, it has valence band more deeper than p-type semiconductor valence band, the wherein mutual ionic communication of semi-conductor type.The heterogeneous material strengthens photocatalytic activity.

Description

Multivalence photocatalysis heterogeneous material for semiconductor

Inventor：

She is bank Baram mountain Mu Bandeng and Zhang Bin

The field of the disclosure

The disclosure describes heterogeneous material, and it is included：P-type semiconductor, it includes mixed valence oxide compound； And n-type semiconductor, it has the mixed valence oxidation of valence band more deeper than p-type semiconductor, wherein n-type semiconductor and p-type semiconductor Compounds are in ionic charge connection.The photocatalysis that these multivalence heterogeneous materials can be used for strengthening catalysis material is lived Property.

The background of the disclosure

Visible-light activated photochemical catalyst can be arranged to the purifying of automatically cleaning, air and water and many other have The application of interest, generally postpones in cloth and does not need any non-renewable cost of energy.Because by using ambient light as too Sun radiation or room light and outdoor optical, photochemical catalyst being capable of decomposing pollutant (such as dyestuff, VOC and NO_x)。 With the quick popularization of the room lighting (such as LEDs and OLEDs) without UV of desirable, the task of top priority is found it will be seen that light The photochemical catalyst of activation is arranged into family, public and commercial location, especially closed place (such as aircraft, public building) In indoor application (such as cleaning room air) in method.In addition, should for other of antimicrobial surface and self-cleaning material With can have wide applicability in food and beverage sevice, communications and transportation, health care and hotel industry.

Single copper simple substance, carbon/carbon-copper composite material have been described with the copper simple substance of oxide-metal combinations, carbon/carbon-copper composite material For useful photocatalysis/antibacterial/antiviral material.Referring to U.S. Patent Publication Nos.2007/0154561,2009/0269269, 2011/0082026 and 2012/0201714；And Qiu, Xiaoqing et al., " Hybrid Cu_XO/ Ti0₂Nanocomposites as risk-reduction materials in indoor environments,” ACSNano, 6 (2)：1609-1618(2012).However, copper simple substance shows that antibacterial activity degrades over time (persistence) and made us The appearance of dislike changes (from Cu metals to black CuO), and both of which is considered as because copper simple substance is in normal use bar It is oxidized under part.Therefore, it is necessary to antibacterial activity with the raising of time life-span.Accordingly, it is desirable to provide antibacterial/antiviral activity and The catalysis material changed without offensive appearance.

Open general introduction

The present disclosure describes heterogeneous material, and it is included：P-type semiconductor, it includes mixed valence oxide compound；And n Type semiconductor, it has valence band more deeper than the valence band of p-type semiconductor, and wherein semiconductor connects in ionic charge each other It is logical.These multivalence heterogeneous materials can be used for strengthen catalysis material photocatalytic activity and for improve persistence (that is, with Time maintains photocatalytic activity).Catalysis material is beneficial to have and/or strengthened：Dyestuff colour fading and/or antibacterial in aqueous solution The decomposition of (light and dark) activity, antiviral activity, VOC (VOC).

Some embodiments include heterogeneous material, and it is included：P-type semiconductor, it includes the first metal oxide chemical combination Thing and the second metal-oxide compound, wherein the first metal-oxide compound and the second metal-oxide compound have phase With the different oxidation state of metal, and wherein p-type semiconductor has p-type valence band；And n-type semiconductor, it has more deeper than p-type valence band N-type valence band, wherein n-type semiconductor is in ionic charge with p-type semiconductor and connects.

Another embodiment also includes noble metal, and the noble metal is in ionic charge company with mixed valence oxide compound It is logical.In another embodiment, noble metal is rhodium, ruthenium, palladium, silver, osmium, platinum or gold.In another embodiment, noble metal is born It is loaded in n-type semiconductor.

Another embodiment also includes the second n-type semiconductor, wherein at least a portion of second n-type semiconductor be with The separation of mixed valence oxide compound ionic charge.In another embodiment, the second n-type semiconductor includes cerium oxide. In another embodiment, cerium oxide is CeO₂.In another embodiment, the second n-type semiconductor includes multiphase TiO₂。

In another embodiment, mixed valence oxide compound includes the same metal in two kinds of different oxidation state Learn element (Cu, Co, Mn, Fe, Ir etc.) it is right, such as copper (I) and copper (II) it is right；Cobalt (II) and cobalt (III) are right；Mn (II) and Mn (III) it is right；Fe (II) and Fe (III) are right；Or Ir (III) and Ir (IV) is right.

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

In another embodiment, p-type semiconductor is substantially dispersed in n-type semiconductor.In another embodiment In, mixed valence oxide compound has 100nm or smaller particle diameter.

In another embodiment, copper (I) and copper (II) compound are Cu_xO compounds.In another embodiment, Cu_xO The valency of compound chemically controls.In another embodiment, copper (I)：The ratio of copper (II) is 10:90 to 90: Between 10.

In another embodiment, p-type semiconductor is the 0.001-10 weight % and p-type semiconductor right and wrong of heterogeneous material The 90-99.999 weight % of homogeneous material.

N-type semiconductor can be any suitable semiconductor, and wherein charge carrier is electronics, such as the donor by dopant With the electronics in conduction band provided.In another embodiment, n-type semiconductor is oxide, comprising cerium, tungsten, tantalum, tin, Zinc, strontium, zirconium, barium, the oxide of indium or aluminium.In another embodiment, n-type semiconductor is Sn-Ti (O, C, N)₂、CeO₂、 KTaO₃、Ta₂O₅、SnO₂、WO₃、ZnO、SrTiO₃、BaTiO₃、ZrTiO₄、In₂TiO₅、Al₂TiO₅Or LiCa₂Zn₂V₃O₁₂.Another In embodiment, n-type semiconductor is Sn-Ti (O, C, N)₂.In another embodiment, n-type semiconductor is Al_2-xIn_xTiO₅, its In 0<x<2.In another embodiment, n-type semiconductor is Zr_1-yCe_yTiO₄, wherein 0<y<1.

In another embodiment, n-type semiconductor can contain titanyl compound.In another embodiment, titaniferous Oxide includes multiphase titanium oxide.In another embodiment, multiphase titanium oxide includes anatase TiO₂Phase and rutile TiO₂The mixture of phase.

In another embodiment, n-type semiconductor is the titanium oxide containing dopant.For example, dopant can be to titanyl The conduction band of compound provides electronics.In another embodiment, n-type semiconductor is doping N, C or the titanium oxide of the two.Another In one embodiment, n-type semiconductor is included by formula (Ti_1-rM_r)(O_2-s-tC_sN_t) represent compound titanium oxide, wherein： M is Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn or Cu or combinations thereof；R is in the range of 0-0.25；S is in 0.001- In the range of 0.1；And t is in the range of 0.001-0.1.

Another embodiment includes photochemical catalyst (Ti_0.99Sn_0.01)(O_2-s-tC_sN_t)、(Ti_0.97Sn₀₃)(O_2-s-tC_sN_t)、 (Ti_0.95Sn_0.05)(O_2-s-tC_sN_t)、(Ti_0.90Sn_0.10)(O_2-s-tC_sN_t)、(Ti_0.85Sn_0.15)(O_2-s-tC_sN_t)、 (Ti_0.985Ni_0.015)(O_2-s-tC_sN_t)、(Ti_0.98Ni_0.02)(O_2-s-tC_sN_t)、(Ti_0.97Ni_0.03)(O_2-s-tCsNt)、 (Ti_0.99Sr_0.01)(O_2-s-tCsNt)、(Ti_0.97Sr_0.03)(O_2-s-tCsNt)、(Ti_0.95Sr_0.05)(O_2-s-tC_sN_t)、 (Ti_0.97Ba_0.03)(O_2-s-tC_sN_t)、(Ti_0.95Ba_0.05)(O_2-s-tC_sN_t)、(Ti_0.94Sn_0.05Fe_0.01)(O_2-s-tC_sN_t)、 (Ti_0.94Sn_0.05Ni_0.01)(O_2-s-tC_sN_t)、(Ti_0.99Fe_0.01)(O_2-s-tC_sN_t)、(Ti_0.95Zn_0.05)(O_2-s-tC_sN_t)、 (Ti_0.77Sn_0.15Cu_0.08)(O_2-s-tC_sN_t)、(Ti_0.85Zn_0.15)(O_2-s-tC_sN_t)、(Ti_0.90Bi_0.10)(O_2-s-tC_sN_t)、 (Ti_0.996V_0.004)(O_2-s-tCsNt)、(Ti_0.984V_0.016)(O_2-s-tCsNt)、(Ti_0.970V_0.03)(O_2-s-tCsNt)、 (Ti_0.997Mo_0.003)(O_2-s-tC_sN_t)、(Ti_0.984Mo_0.016)(O_2-s-tC_sN_t)、(Ti_0.957Mo_0.043)(O_2-s-tC_sN_t)、 (Ti_0.97W_0.03)(O_2-s-tC_sN_t)、(Ti_0.95W_0.05)(O_2-s-tC_sN_t)、(Ti_0.996V_0.004)(O_2-s-tC_sN_t)、(Ti_0.984V_0.016) (O_2-s-tC_sN_t) or (Ti_0.970V_0.03)(O_2-s-tC_sN_t)。

Some embodiments include the method for chemical decomposition compound, and methods described includes：In the presence of light, describedization is made Chemical combination thing is exposed to the photochemical catalyst for including homogeneous material as described herein.In some embodiments, chemical compound is Pollutant, such as VOC.

Some embodiments include the method for killing microorganism, and methods described includes：In the presence of light, microbial exposure is made In the photochemical catalyst for including homogeneous material as described herein.

Particular implementation as described herein includes the method for load mixed valence compound.This method may include：To mixing Dispersant is added in valency type compound so that the more positive charges of surface band of n-type compound；Attractant is added into n-type compound So that the surface charge negative value of n-type semiconductor is bigger；With at a temperature of the doping temperature less than mixed valence compound, make band The material of different electric charges is mutually mixed.

Brief description

Figure 1A is the schematic diagram for showing relation between the conduction band of metal material and valency energy band.

Figure 1B is the schematic diagram for showing relation between the conduction band of semi-conducting material and valency energy band.

Fig. 1 C are the schematic diagrames for showing relation between the conduction band of non-conductive materials and valency energy band.

Fig. 2 is to show that the conduction band of various compounds as described herein and valency can the schematic diagrames with level.

Fig. 3 show a kind of embodiment of p-type and n-type composite as described herein X-ray diffraction pattern and individually N-type material a kind of embodiment X-ray diffraction pattern.

Fig. 4 shows the X-ray diffraction pattern and list of the another embodiment of p-type and n-type composite as described herein The X-ray diffraction pattern of the another embodiment of only n-type material.

Fig. 5 shows the X-ray diffraction pattern and list of the another embodiment of p-type and n-type composite as described herein The X-ray diffraction pattern of the another embodiment of only n-type material.

Fig. 6 shows the embodiment of p-type and n-type composite more as described herein and the reality of single n-type material Apply mode (Ti (OCN)₂:Sn diffusing reflection spectrum).

Fig. 7 shows the another embodiment of p-type and n-type composite more as described herein and single n-type material Another embodiment (the CeO of material₂) diffusing reflection spectrum.

Fig. 8 shows the another embodiment of p-type and n-type composite more as described herein and single n-type material The diffusing reflection spectrum of the another embodiment of material.

Fig. 9 chart shows the acetaldehyde point by various optic catalytic composite materials (Ex-1A and CE-1) as described herein Solution.

Figure 10 chart is shown after the 800 lux visible rays from fluorescent lamp, by as described herein The antibacterial activity (CFU/ samples) to E.Coli of various optic catalytic composite materials (Ex-1A and CE-1).

Figure 11 chart is shown after the 800 lux visible rays from fluorescent lamp, by as described herein The antibacterial activity (CFU/ samples) to E.Coli of various optic catalytic composite materials (Ex-4 and CE-2).

Figure 12 A chart show 85 DEG C and 85% relative humidity (RH) under handle 7 days before and after, pass through light The antibacterial activity persistence to E.coli of the enhancing of catalytic composite materials (Ex-1).

Figure 12 B chart is shown handled 20 minutes at 300 DEG C before and after, pass through optic catalytic composite material (Ex- 7) the antibacterial activity persistence to E.coli of enhancing.

Figure 13 chart is shown by various optic catalytic composite materials (embodiment 1 as described herein and CE-1 and band Have and without Cu_xThe rutile TiO of O loads₂) natural blue dyestuff fade.

Figure 14 chart is shown by various optic catalytic composite materials (Ex-12,13,15,16 and CE- as described herein 6) acetal dehyde decomposition.

Figure 15 chart is shown by various optic catalytic composite materials (embodiment 19 and non-loaded SnO₂) it is natural The dyestuff of blueness fades.

Figure 16 chart is shown to be faded by the dyestuff of the natural blue of various optic catalytic composite materials (Ex-18).

Figure 17 chart shows CE-0 (0.25 weight % CuO+0.12 weight % Cu₂O+0.5 weight % doping Sn Ti (OCN)₂Photochemical catalyst) physical mixture to E.coli kill performance influence.

Figure 18 chart shows Ex-7A (0.5 weight % of load Cu_xO aluminum oxide (non-photochemical catalyst)) to antibacterial The influence of performance (E.coli kills research).

Figure 19 chart shows Ex-1B (0.5 weight % of load Cu_xO doping Sn Ti (OCN)₂Photochemical catalyst) it is right The influence of anti-microbial property (E.coli kills research).

Figure 20 chart shows Ex-1 (1 weight % of load Cu_xO doping Sn Ti (OCN)₂) to anti-microbial property Cooperative effect (E.coli kills research).

Figure 21 chart shows Ex-1 (1 weight % of load Cu_xO doping Sn Ti (OCN)₂) to anti-microbial property The persistent result of enhancing (E.coli kills research).

Figure 22 chart shows Cu_xO/P25 and Cu_xO/Al₂O₃To the cooperative effect of anti-microbial property, (E.coli is killed and ground Study carefully).

Figure 23 chart shows Cu_xO/P25 and Cu_xO/Al₂O₃The persistent result of enhancing to anti-microbial property (E.coli kills research).

Describe in detail

The present disclosure describes heterogeneous material, and it includes the p-type semiconductor containing mixed valence oxide compound.P-type half Conductor has p-type valence band.Heterogeneous material also includes the n-type semiconductor with n-type valence band, and the n-type valence band is than p-type valence band Deeper valence band.In heterogeneous material, n-type semiconductor is in ionic charge with mixed valence oxide compound and connected.These Multivalence heterogeneous material can be used for the photocatalytic activity for strengthening catalysis material and for improving persistence (that is, with time dimension Hold photocatalytic activity).Catalysis material is beneficial to have and/or strengthened：In aqueous solution dyestuff fade and/or antibacterial (light and Secretly) the decomposition of activity, antiviral activity, VOC (VOC).

As shown in fig. 1, conduction band 10 is to be enough to make that electronics is broken away from and the combination of its atom is so as to being used as " delocalized electron " The electron energy scope moved freely in the atomic lattice of material.In the semiconductors, valence band 20 is highest electron energy model Enclose, wherein electronics normal presence under absolute zero temperature.Valence electron is substantially combined with single atom, and this is with conducting electronics (being found in semiconductor) is on the contrary, conduction electronics can more freely move in the atomic lattice of material.In the electronics of material On band structure chart, valence band 20 is normally at below conduction band, passes through band gap 30 and conduction band point in insulator and semiconductor From.In some materials, conduction band is essentially without the recognizable energy gap for separating its conduction band and valence band.For example, work as valency Band potential energy (level energy) is higher than conduction band potential energy or when negative value is smaller, and conduction band and valence band actually can be overlapping (overlapping 25)。

Various materials can be classified by their band gap；For example, by the difference between valence band 20 and conduction band 10 come Sort out.In non-conductor (for example, insulator), conduction band has the much higher energy of rate of exchange band, therefore in order that insulator has Effect is conductive, to expend huge multi-energy to move valence electron.These insulators are considered to have non-zero band gap.Conductor is (for example, gold Category) there are many free electrons under normal circumstances, wherein, conduction band 10 and valence band 20 overlapping 25, i.e., no band gap, therefore come Mobile valence electron expends seldom or not expended extra applied energy.In the semiconductors, band gap very little, about 200nm- 1000nm.Although wanting to be limited to theory, this is considered as that the electronics for making semiconductor moves to another energy level and conduction from valence band The reason for lacking energy (as heat or light) relatively will be expended；Therefore, it is named as semiconductor.

In some embodiments, there is provided heterogeneous material, it is included：P-type semiconductor, it includes mixed valence oxidation materialization Compound, the compound have p-type conduction band and p-type valence band；With the n-type semiconductor of separation, it has n-type valence band, the n Type valence band is more deeper than p-type valence band, energy is lower or negative value is bigger.N-type semiconductor should be in ionic charge company with p-type semiconductor Logical, this represents that ionic charge can be transferred to mixed valence oxide compound from n-type semiconductor, or from mixed valence oxide compound It is transferred to n-type semiconductor.The example of suitable conduction band and valence band is shown in Fig. 2.Although being not intending to be bound by theory, but if The valence band of n-type semiconductor is more deeper than the valence band of p-type semiconductor or negative value is bigger, then electronics can be more easily from n-type compound It is transferred to p-type compound.If material is in ionic communication, electronics can be transferred to next chemical combination from a compound Thing, so as to regenerate higher price compound to compared with sub-compound.For example, Cu²⁺It can be recirculated by this mechanism and be Cu¹⁺.In some embodiments, by the material load in ionic communication on each other.By load, it is single that material retains them Only characteristic；For example, Cu_xO (p-type semiconductor with) and TiO_2,、Ti(OCN)₂:Sn etc. (n-type semiconductor) is separated.In particular implementation In mode, a kind of material on the surface, contact or close to another material, with adulterate on the contrary, separated with another Material Physics, Ionic charge separates or blending (physical mixed).In some embodiments, can be shown by the transmitted electron of p-type and n-type material Micro mirror (TEM) is checked to judge this contact and/or separation.In other embodiments, heterogeneous material is incorporated into chemical combination In thing matrix；For example, in incorporation compound/crystal lattices.

Heterogeneous material can include any suitable p-type semiconductor, including wherein charge carrier is effectively positively charged Any semiconductor in hole.In addition to it may carry some holes of positive charge substantially, these holes may be present in p-type valence band In, the p-type valence band can be filled substantially with electronics.In some embodiments, p-type semiconductor can include mixed with p-type valence band Conjunction valency oxide compound.In some embodiments, mixed valence oxide compound includes the mixed valence of same metal element It is right, 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 And Ir (IV) (III)；With combinations thereof.In certain embodiments, copper (I) and copper (II) compound can be Cu_xOization Compound.In certain embodiments, mixed valence oxide compound may include Cu¹⁺And Cu²⁺.Mixed valence oxide compound Ratio can be 10%-90%：90%-10%.Specific ratio may also include：15%：85%；20%：80%；25%： 75%；30%：70%；35%：65%；40%：60%；45%：55%；50%：50%；55%：45%；60%：40%； 65%：35%；70%：30%；75%：25%；80%：20%；With 85%：15%.

In certain embodiments, mixed valence oxide compound is that ratio is 10%-90%Cu¹⁺：90%-10%Cu²⁺ Cu¹⁺：Cu²⁺。Cu¹⁺:Cu²⁺Ratio can also be about 10%:90%- about 30%:70%；About 15%:85%- about 25%: 75%；About 15%:85%；About 20%:80%；About 25%:75%；About 30%:70%；About 35%:65%；About 40%:60%； About 45%:55%；About 50%:50%；About 55%:45%；About 60%:40%；About 65%:35%；About 70%:30%；About 75%:25%；About 80%:20%；Or about 85%:15%.In some embodiments, ratio is Cu¹⁺:Cu²⁺Weight %. In some embodiments, ratio is Cu¹⁺:Cu²⁺Mole %.

In some embodiments, wherein n-type semiconductor is in ionic charge with p-type semiconductor and connected, p-type semiconductor quilt (loaded) is loaded to n-type semiconductor.In some embodiments, wherein n-type semiconductor is in ion-conductance with p-type semiconductor Lotus connects, and p-type semiconductor can be embedded in, be layered on, being deposited in n-type semiconductor and/or being contacted with n-type semiconductor. In some embodiments, p-type semiconductor mixed valence compound is substantially dispersed in n-type semiconductor.Mixed valence compound Particle diameter be smaller than 200nm；Less than 190nm；Less than 180nm；Less than 170nm；Less than 160nm；Less than 150nm；It is less than 140nm；Less than 130nm；Less than 120nm；Less than 110nm；Less than 100nm；Less than 90nm；Less than 80nm；Less than 70nm；It is less than 60nm；Less than 50nm；Less than 40nm；Less than 30nm；Less than 20nm；Or, less than 10nm.In a particular implementation, mix The particle diameter of conjunction valency compound is 100nm or smaller.

In some embodiments, p-type semiconductor forms 0.001-10 weight % heterogeneous material and n-type semiconductor structure Into 99.999-90 weight % heterogeneous material.In extra embodiment, p-type semiconductor forms the non-of 0.001 weight % Homogeneous material；0.005 weight % heterogeneous material；0.01 weight % heterogeneous material；0.05 weight % heterogeneous material Material；0.1 weight % heterogeneous material；0.5 weight % heterogeneous material；1 weight % heterogeneous material；2 weight %'s Heterogeneous material；3 weight % heterogeneous material；4 weight % heterogeneous material；5 weight % heterogeneous material；6 weights Measure % heterogeneous material；7 weight % heterogeneous material；8 weight % heterogeneous material；9 weight % heterogeneous material； Or 10 weight % heterogeneous material.In extra embodiment, n-type semiconductor forms 90 weight % heterogeneous material Material；91 weight % heterogeneous material；92 weight % heterogeneous material；93 weight % heterogeneous material；94 weight %'s Heterogeneous material；95 weight % heterogeneous material；96 weight % heterogeneous material；97 weight % heterogeneous material；98 Weight % heterogeneous material；99 weight % heterogeneous material；99.1 weight % heterogeneous material；99.2 weight %'s is non- Homogeneous material；99.3 weight % heterogeneous material；99.4 weight % heterogeneous material；99.5 weight % heterogeneous material Material；99.6 weight % heterogeneous material；99.7 weight % heterogeneous material；99.8 weight % heterogeneous material；Or 99.5 weight % heterogeneous material；.

In some embodiments, p-type semiconductor includes the mixture of Cu oxide, such as the first Cu oxide compound With the second Cu oxide, such as Cu (I) compound is (for example, Cu₂) and Cu (II) compound (for example, CuO) O.In some implementations In mode, p-type semiconductor includes weight：Weight or mole：Molar ratio [Cu (I):Cu (II)] it is about 1:9- about 3:7th, about 1: 3- about 1:6 or about 1:3- about 1:4 Cu (I) is (for example, Cu₂) and Cu (II) (for example, CuO) O.

Some embodiments include the combination of the p-type semiconductor and n-type semiconductor of the last period, and the n-type semiconductor is titanium Oxide or doped tin or titanium oxide are (for example, the TiO with more than one phase₂) Ti (O, C, N)₂.In some embodiment party In formula, this TiO₂Can have two kinds of phases, such as rutile TiO₂With anatase TiO₂.In some embodiments, n-type is partly led Body can be the Anatases of about 70%- about 90% and the Rutile Type TiO of 10%- about 30%₂, the Anatases of about 80%- about 90% With the Rutile Type TiO of 20%- about 30%₂, the Anatases of about 75%- about 80% and the Rutile Type TiO of 15%- about 20%₂Or About 83% Anatase TiO₂With 17% Rutile Type TiO₂.Some embodiments include the p-type semiconductor and n-type half of the last period The combination of conductor, the n-type semiconductor are tin-oxides.

Semiconductor for including p-type semiconductor and n-type semiconductor, wherein there is the p-type semiconductor Cu oxide to mix Compound and the n-type semiconductor are titanium oxide or Doped with Titanium or titanium oxide (for example, the TiO with more than one phase₂) Ti (O, C, N)₂, in some embodiments, Cu oxide can be for the n- and about 0.1%- of p-type semiconductor gross weight about 5%th, about 0.2%- about 2%, about 0.2%- about 1.5%, about 0.5% or about 1%.

In some embodiments, p-type semiconductor is loaded in n-type semiconductor.In some embodiments, n-type half Conductor is oxide, and the oxide includes the oxidation for the element that can be cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium or aluminium Thing, it has than p-type semiconductor to the deeper valence band of valence band.In some embodiments, n-type semiconductor can be anatase, Rutile, wurtzite, spinelle, perovskite, pyrochlore, garnet, zircon and/or aluminium pseudobrookite (tialite) phase material Material or their mixture.In these options it is every kind of have semiconductor applications in those of ordinary skill understood its generally contain Justice.The comparison of the standard items and the X-ray diffraction pattern of the sample of production that provide is whether to include specific phase available for determination sample One of numerous methods.Example standards include national standard and technical research institute (NIST) (Gaitherburg, Maryland, The U.S.) and/or joint committee (ICDD, former Joint Committee on Powder Diffraction Standards [JCPDS]) Those XRD spectrums that (NewtownSquare, Pennsylvania, the U.S.) is provided.In some embodiments, perovskite can To be perovskite oxide.In some embodiments, perovskite oxide may include FeTiO_3、YFeO_3、LuRhO_3、BaSnO_3、 Ba_0.8Ca_0.2TiO_3、CdSnO_3、LaRhO_3、LaRhO_3、LaMnO_3、CoTiO_3、CuTiO_3、MgTiO_3、ZnTiO_3、BiNb_1-xTa_xO₄(its Middle x=0-1.00) or InNb_1-xTaxO₄(wherein x=0-1.00).

In extra embodiment, n-type semiconductor can include cerium, tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, niobium, vanadium, Iron, cadmium, germanium and/or aluminum oxide.N-type semiconductor can also include CeO₂；MgTa₂O₆；BaTa₂O₆；SrTa₂O₆；Ta₂O_5； FeTa₂O₆；Hg₂Ta₂O₇；Hg₂Nb₂O₇；Hg₂Ta_vNb_1-vO₇；K₃Ta₃Si₂O₁₃；K₂LnTa₅O₁₅；WO₃；ZnO；SrTiO₃；SrNb₂O₇； SrTa₂O₇；SrTaNbO₇；Sr₂FeNbO₆；Sr₃FeNb₂O₉；TiO₂；SnO₂；BaTiO₃；FeTiO₃；CdFe₂O₄；MnTiO₃； Cs₂Nb₄O₁₁；KNbO₃；Sr₂FeNbO₆；Sr₃FeNb₂O₉；NiNb₂O₆；CoNb₂O₆；ZnNb₂O₆；Nb₂O₅；K₄Nb₆O₁₇；Rb₄Nb₆O₁₇； CuTiO₃；BiO₃；In₂O₃；LiTaO₃；NiTiO₃；In₂TiO_5；Al₂TiO₅；Al_2-xIn_xTiO₅；ZrTiO_4；Zr_1-yCe_yTiO₄； LiCa₂Zn₂V₃O₁₂；Cd₂SnO₄；CdIn₂O₄；Cd₂GeO₄；Bi₂W₂O₉；Bi₂WO₆；Bi₃TiNbO₉；ACrO₄, wherein A can be Sr, Ba or combinations thereof；CuMnO₂；PbWO₄；CuFeO₂；InVO₄；MVWO₆, wherein M can be Li, Ag or combinations thereof； Bi₂MNbO₇, wherein M can be Al, Ga, In, Y, rare earth element, Fe or combinations thereof；Zr₂WO₆；PbWO₄；SnWO₄； Bi₂W₂O₉；Na₂W₄O₁₃；And/or MWO₄, wherein M can be Ca, Zn, Cu or combinations thereof.

In some embodiments, n-type semiconductor can be scherbinaite garnet semiconductor light-catalyst.In some embodiments In, formula can be used：(A_1-xO_x)₃(M)₂(V₃)O₁₂(wherein 0<x<1) scherbinaite garnet semiconductor light-catalyst is represented.In some realities Apply in mode, (A_1-xO_x)₃(M)₂Accumulation ionic charge be+9.In some embodiments, A⁺Can be Li⁺、Cu⁺、Na⁺、 K⁺、Ti⁺、Cd²⁺、Ca²⁺、Sr²⁺、Pb²⁺、Y³⁺、Bi³⁺、Ln³⁺Or combinations thereof.In some embodiments, M can be Li⁺、 Ni²⁺、Mg²⁺、Co²⁺、Cu²⁺、Zn²⁺、Mn²⁺、Cd²⁺、Cr³⁺、Fe³⁺、orSc³⁺Or one kind or any in combinations thereof.

In some embodiments, n-type semiconductor can be scherbinaite garnet semiconductor light-catalyst.In some embodiments In, formula 1 can be used：(A²⁺)₃(M⁺M²⁺)(V₃)O₁₂To represent scherbinaite garnet semiconductor light-catalyst.In some embodiments, Scherbinaite garnet semiconductor light-catalyst can be Ca₃LiZnV₃O₁₂And/or Sr₃LiZnV₃O₁₂。

In some embodiments, n-type semiconductor can be mixing titanate.Term " mixing titanate " refers to including Ti, O and the compound of at least another element (for example, Ca, Cu, Mg or La).In some embodiments, mixing titanate can To be CaCu₂Ti₃O₁₂(perovskite titanate)；MgTi₂O₅(pseudobrookite hydrochlorate)；And/or La₂Ti₂O₇(pyrochlore titanate). In some embodiments, Ti oxides can include anatase and rutile TiO₂Mixture.

In some embodiments, n-type semiconductor may include to mix Cu oxide.Mixing Cu oxide refers to including Cu, O and the n-type semiconductor different from copper and another element of oxygen.In some embodiments, mixing Cu oxide can be with It is CuMnO₂Or CuFeO₂。

In some embodiments, n-type semiconductor can be single or mixing ferrite.In some embodiments In, mixing ferrite can be α-Fe₂O₃；MFe₂O4, wherein M are Mg, Zn, Ca, Ba or combinations thereof；Ca₂Fe₂O₅、 MFe₁₂O₁₉, wherein M is Sr, Ba or combinations thereof；Sr₇Fe₁₀O₂₂、MFeO_2.5+x, wherein M is Sr, Ba or combinations thereof； Sr₃Fe₂O_6.16；Bi_1.5Pb_0.5Sr₂BiFe₂O_9.25；Pb₂Sr₂BiFe₂O_9+y；Bi₂Sr₂BiFe₂O_9+y；And/or Bi_1.5Pb_0.5Sr₄Fe₂O_10.04。

In some embodiments, n-type semiconductor can be loaded Cu_xO nitrogen oxides semiconductor light-catalyst.One In a little embodiments, nitrogen oxides semiconductor light-catalyst can include TaON；MTaO₂N, wherein M be Ca, Sr, Ba or they Combination；SrNb₂O_7-xN_x；(Ga_1-xZn_x)(N_1-xO_x)；And/or (Zn_1+xGe)(N₂O_x)。

In some embodiments, n-type semiconductor can be loaded Cu_xO sulfide, selenides or sulfoselenide is partly led Body photochemical catalyst.In some embodiments, sulfide, selenides or sulfoselenide semiconductor light-catalyst can include Cd (S_y, Se_1-y), wherein 0<y<1；(Cd,Zn(S_y,Se_1-y), wherein 0<y<1；(AgIn)_xZn_2(1-x)(S_y,Se_1-y)₂, wherein 0<y<1； (CuIn)_xZn_2(1-x)(S_y,Se_1-y)₂, wherein 0<y<1；(CuAgIn)_xSn_2(1-x)(S_y,Se_1-y)₂, wherein 0<y<1；And/or Sm₂Ti₂S₂O₅。

In certain embodiments, n-type semiconductor includes formula Al_2-xIn_xTiO₅Representative compound, wherein x is 0-2's In the range of (0<x<2).In other particular implementations, n-type semiconductor includes formula Zr_1-yCe_yTiO₄Representative compound, its Middle y is (0 in the range of 0-1<y<1).In certain embodiments, n-type semiconductor is titanium oxide, and it has by adulterating quilt The valence band of control.In certain embodiments, n-type semiconductor is doping N or C or the titanium oxide of the two.In some embodiment party In formula, titanium oxide includes formula (Ti_1-rM_r)(O_2-s-tC_sN_t) representated by compound, wherein M be Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn, Cu or combinations thereof；R is in the range of 0-0.25；S is in the range of 0.001-0.1；And t is in 0.001- In the range of 0.1.In some embodiments, r is not more than 0.20.In some embodiments, r can be more specifically 0； 0.01；0.02；0.03；0.04；0.05；0.06；0.07；0.08；0.09；0.10；0.11；0.12；0.13；0.14；0.15； 0.16；0.17；0.18；0.19；0.20；0.21；0.22；0.23；0.24 or 0.25.In some embodiments, s can be more specific Ground is 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 implementations In mode, t can be more specifically 0.001；0.005；0.01；0.02；0.03；0.04；0.05；0.06；0.07；0.08；0.09； Or 0.1.

Material is also described in the CO-PENDING submitted on January 14th, 2013 and the application specified jointly, series number 13/741, In 191, application description as described in photocatalysis compound and/or composition, which is incorporated by reference, to be integrally incorporated.In some realities Apply in mode, M is Sn, Ni, Sr, Ba, Fe, Bi or combinations thereof.In some embodiments, r is 0.0001-0.15's In the range of.In some embodiments, M is Sn.In some embodiments, r is at least 0.001.In some embodiments, N-type semiconductor includes (Ti_0.99Sn_0.01)(O_2-s-tCsNt)、(Ti_0.97Sn_0.03)(O_2-s-tC_sN_t)、(Ti_0.95Sn_0.05)(O_2-s- _tC_sN_t)、(Ti_0.90Sn_0.10)(O_2-s-tC_sN_t)、(Ti_0.85Sn_0.15)(O_2-s-tC_sN_t)、(Ti_0.985Ni_0.015)(O_2-s-tC_sN_t)、 (Ti_0.98Ni_0.02)(O_2-s-tC_sN_t)、(Ti_0.97Ni_0.03)(O_2-s-tC_sN_t)、(Ti_0.99Sr_0.01)(O_2-s-tC_sN_t)、(Ti_0.97Sr_0.03) (O_2-s-tC_sN_t)、(Ti_0.95Sr_0.05)(O_2-s-tC_sN_t)、(Ti_0.97Ba_0.03)(O_2-s-tC_sN_t)、(Ti_0.95Ba_0.05)(O_2-s-tC_sN_t)、 (Ti_0.94Sn_0.05Fe_0.01)(O_2-s-tC_sN_t)、(Ti_0.94Sn_0.05Ni_0.01)(O_2-s-tC_sN_t)、(Ti_0.99Fe_0.01)(O_2-s-tC_sN_t)、 (Ti_0.95Zn_0.05)(O_2-s-tC_sN_t)、(Ti_0.77Sn_0.15Cu_0.08)(O_2-s-tC_sN_t)、(Ti_0.85Zn_0.15)(O_2-s-tC_sN_t)、 (Ti_0.90Bi_0.10)(O_2-s-tC_sN_t)、(Ti_0.996V_0.004)(O_2-s-tC_sN_t)、(Ti_0.984V_0.016)(O_2-s-tC_sN_t)、 (Ti_0.970V_0.03)(O_2-s-tC_sN_t)、(Ti_0.997Mo_0.003)(O_2-s-tC_sN_t)、(Ti_0.984Mo_0.016)(O_2-s-tC_sN_t)、 (Ti_0.957Mo_0.043)(O_2-s-tC_sN_t)、(Ti_0.97W_0.03)(O_2-s-tC_sN_t), and/or (Ti_0.95W_0.05)(O_2-s-tC_sN_t).At some In embodiment, n-type semiconductor includes (Ti_0.996V_0.004)(O_2-s-tC_sN_t)、(Ti_0.984V_0.016)(_O2-s-tC_sN_t), and/or (Ti_0.970V_0.03)(O_2-s-tC_sN_t)。

In some embodiments, wherein heterogeneous material includes the p-type semiconductor being supported in n-type semiconductor, described Heterogeneous material also includes the second n-type semiconductor, wherein at least a portion of second n-type semiconductor is and p-type semiconductor Ionic charge separation.In some embodiments, at least a portion of the second n-type semiconductor can be with p-type semiconductor ion thing Reason separation, ionic charge separation, admix and/or do not load p-type semiconductor.In some embodiments, the second n-type semiconductor can To be those n-type semiconductors described in any other places in this application.In some embodiments, ionic charge is separated or mixed The n-type semiconductor of sum can include CeO₂And/or multiphase n-type semiconductor compound.In some embodiments, multiphase n-type is partly led Body compound includes Anatase and Rutile Type compound.In some embodiments, multiphase n-type semiconductor compound can be with It is titanium oxide.In some embodiments, Anatase can be 2.5%- about 97.5%, 5%- about 95%, and/or about 10%- about 90%；And Rutile Type can be 97.5%- about 2.5%, 95%- about 5%, and/or about 10%- about 90%.Properly The non-limitative example of material includes but is not limited to the TiO sold by Evonik with trade (brand) name P25₂Mixture (83% rutile titania Ore deposit phase TiO₂+ 17% Rutile Type TiO₂).In some embodiments, with being carried on WO₃On p-type semiconductor physical mixed N-type semiconductor can include CeO₂、TiO₂、SrTiO₃And/or KTaO₃.In some embodiments, with being carried on multiphase n-type half The n-type semiconductor of p-type semiconductor physical mixed in conductor compound (for example, P25) can partly be led comprising unsupported multiphase n-type Body compound (for example, P25).In some embodiments, the p-type semiconductor with being carried in multiphase n-type semiconductor compound The n-type semiconductor of physical mixed can include CeO₂、TiO₂、SrTiO₃And/or KTaO₃.In some embodiments, n-type semiconductor Can be inorganic.In some embodiments, inorganic n-type semiconductor can be oxide, such as metal dioxide, including CeO₂、TiO₂Etc..In some embodiments, n-type semiconductor can include SiO₂、SnO₂、Al₂O₃、ZrO₂、Fe₂O₃、Fe₃O₄、 NiO、Nb₂O₅, and/or CeO₂。

In some embodiments, n-type semiconductor can be RE_kE_mO_n, wherein RE is rare earth element, E be a kind of element or The combination of element, O are oxygen, and 1≤k≤2,2≤m≤3, and 0≤n≤3.In some embodiments, n-type semiconductor can be RE_pO_q, wherein RE can be rare earth element；P can be more than or equal to 1 and less than or equal to 2, or can be between 1 and 2；Q can be more than or Equal to 2 and less than or equal to 3, or can be between 2-3.The example of suitable rare earths element includes scandium, iridium and group of the lanthanides and actinides. Lanthanide series includes the element that atomic number is 57-71, and actinides includes the element that atomic number is 89-103.In some realities Apply in mode, n-type semiconductor can be Ce_xZr_yO₂, wherein y/x ratios=0.001-0.999.In some embodiments, n-type Semiconductor can be cerium.In some embodiments, n-type semiconductor can be CeO_a(a≤2).In some embodiments, n Type semiconductor can be ceria (CeO₂)。

In some embodiments, n-type semiconductor can be non-oxidized substance.In some embodiments, n-type semiconductor can To be carbide and/or nitride.In some embodiments, carbide can be carborundum.

In some embodiments, n-type semiconductor is (for example, CeO₂) with loading WO₃P-type semiconductor (for example, Cu_xO- WO₃) physical mixture molar ratio can be 0-99% n-type semiconductor：100%-1% p-type semiconductor (load WO₃ Cu_xO).In some embodiments, n-type semiconductor is (for example, CeO₂) with loading WO₃P-type semiconductor (for example, Cu_xO- WO₃) physical mixture molar ratio can be 25-75% (and middle any integer) n-type semiconductor：75%- The load n-type material of 25% (and middle any integer) is (for example, WO₃) p-type semiconductor.In some embodiments, n-type Semiconductor is (for example, CeO₂) with loading WO₃The molar ratio of physical mixture of p-type semiconductor can be 40-60% (in and Between any integer) n-type semiconductor：60%-40% (and middle any integer) load n-type material is (for example, WO₃) P-type semiconductor.

In some embodiments, heterogeneous material can also include and be in ionic charge company with mixed valence oxide compound Logical noble metal.In some embodiments, noble metal is loaded in n-type semiconductor.In some embodiments, noble metal Rhodium, ruthenium, palladium, silver, osmium, platinum and/or gold or their mixture can be but not limited to.In one embodiment, noble metal It is platinum.

In some embodiments, loading the method for mixed valence compound can be：To attractant (attracting Agent p-type precursor is added in) so that the surface charge negative value of n-type semiconductor is bigger, wherein p-type precursor includes copper cation network Compound.In some embodiments, loading the method for mixed valence compound can be：Attractant is added into n-type compound； At a temperature of doping temperature less than mixed valence compound, n-type and p-type precursor are mutually combined.In some embodiments, institute It is further comprising the steps of to state method：Dispersant is added into n-type compound so that the more positive charges of surface band of n-type compound.

In some embodiments, loading the method for mixed valence compound can be：Dispersant is added into n-type compound So that the more positive charges of surface band of n-type compound；P-type precursor, wherein p-type precursor are added into dispersant and n-type compound Include copper cationic complex；Attractant is added into n-type compound so that the surface charge negative value of n-type semiconductor is bigger；With And at a temperature of the doping temperature less than mixed valence compound, the material with different electric charges is mutually combined.

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

In some embodiments, during mixed valence oxide synthesizes, valency control material is in company with the material with different electric charges Material adds to control mixed valence oxide together.In some embodiments, valency control material is gentle reducing agent.At some In embodiment, valency control material can be at least one of sugar, hydrazides, amino acid, and/or acid amides.In some embodiment party In formula, acid amides can be urea.In some embodiments, sugar can be sucrose, fructose, and/or glucose.In some implementations In mode, sugar is glucose.In some embodiments, hydrazides can be carbohydrazide, the hydrazine of oxalyl two, maleic acid hydrazide, two formyls Base hydrazine or diformyl triazine (tetraformyl trisazine).In some embodiments, amino acid can be at least one Kind proteinogen or natural amino acid.In some embodiments, amino acid can be aliphatic amino acid (for example, glycine, the third ammonia Acid, valine, leucine and/or isoleucine).In some embodiments, amino acid can be the amino of hydroxyl or sulphur Sour (for example, serine, cysteine, threonine and/or methionine).In some embodiments, amino acid can be ring (for example, proline) of shape.In some embodiments, amino acid can be aromatics (for example, phenylalanine, tyrosine and/ Or tryptophan).In some embodiments, amino acid can be alkaline (for example, histidine, lysine and/or arginine). In some embodiments, amino acid can be acid or acid amides (for example, aspartate (ester), glutamate (ester), day Winter acid amides and/or glutamine).In some embodiments, amino acid can be that selenocysteine and/or pyrroles rely ammonia Acid.In some embodiments, amino acid can be non-proteinogenic amino acids.In some embodiments, non-proteinogen amino Acid includes those (for example, carnitine, the GABA) not found in protein.In some embodiments, non-proteinogen amino Acid can be those (for example, hydroxyproline and the selenomethionines) separated by the cellular machineries of standard.In some implementations In mode, amino acid may be dissolved in water.In some embodiments, amino acid may be dissolved in 90 DEG C of water.In some implementations In mode, amino acid is substantially dissolved completely in 90 DEG C of water.Term is " dissolvable " to be had known to those of ordinary skill in the art Usual implication.

In some embodiments, mixed valence oxide compound is (for example, Cu¹⁺Compound and Cu²⁺Compound) ratio It can be controlled by the method for loading to Cu in p-type semiconductor, methods described includes adding attractant.In some embodiments In, can control the attractant of the ratio of mixed valence oxide compound can include monose and alkali cpd.In some embodiment party In formula, monose can be glucose.In some embodiments, glucose can be D-Glucose and/or L- glucose.One In a little embodiments, glucose：NaOH ratio can be 10%-90%：90%-10%.Specific ratio may also include： 15%：85%；20%：80%；25%：75%；30%：70%；35%：65%；40%：60%；45%：55%；50%： 50%；55%：45%；60%：40%；65%：35%；70%：30%；75%：25%；80%：20%；With 85%：15%. In some embodiments, alkali can be NaOH.Chemically control Cu_xThe valency of O compounds.

In some embodiments, attractant can be such agent, and it provides enough hydroxidions so that the pH of total solution Between 8.0-9.0.In some embodiments, attractant can be strong acid.In some embodiments, attractant can be 4-7M highly basic.In some embodiments, attractant is 6M NaOH.

In some embodiments, p-type precursor can be the compound for being substantially free of sodium.In some embodiments, The compound for being substantially free of sodium can be copper cationic complex.In some embodiments, copper cationic complex can be with Be double (ethylenediamine) copper (II) (BEDCuII), Copper (II) tetramines chloride, Copper (II) tetramine sulfate, and/or Copper (II) tetramine hydroxide and/or their mixture.In some embodiments, compound can be double (second two Amine) copper (II).BEDCuII structure is as follows：

In some embodiments, the doping temperature of mixed valence compound is between 150 DEG C -700 DEG C.In some embodiment party In formula, less than mixed valence compound doping temperature be less than 175 DEG C, less than 150 DEG C, less than 125 DEG C.In some embodiments In, mixing temperature is between 75 DEG C -125 DEG C.In some embodiments, mixing temperature be 80 DEG C, 85 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C or 120 DEG C.

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

In some embodiments, the heterogeneous material has photocatalytic activity.Heterogeneous material can antibacterial (light and Secretly)；It is antiviral；Being capable of decomposing volatile organic compound (VOC)；And/or food additives dyestuff can be made to fade.Food additive Add agent dyestuff suitable non-limitative example include natural blue powder (Color Maker, Anaheim, California, The U.S.) and/or No. 2 (blue No.2) fabricated food additive dyestuffs of FD＆C bluenesss (synthesis blue powder, Chromatech, Inc., Michigan, the U.S.).Heterogeneous material as described herein can also strengthen the persistence (effective time) of catalysis material.

Skilled addressee will appreciate that judge heterogeneous material whether the method for antibacterial (light), for example, heterogeneous Material is exposed to after visible ray.In one embodiment, antibacterial exposure causes to reduce at least 10% (residue 90%), at least 50% (residue 50%), at least 99% (residue at least 1%), at least 99.9% (residue at least 0.1%) or at least 100% are (surplus Remaining 0%).Whether an example of antibacterial (light) can be the amount for existing by assessing bacterium to measure heterogeneous material；For example, Heterogeneous material is contacted and exposed to bacterium after visible ray, the reduction of the amount of bacterium be present.For example, can evaluate sample quilt After exposing the persistently predetermined period, wherein the amount of bacterium be present.In some embodiments, sample can be exposed 15 minutes, 30 minutes, 1 hour, 2 hours, 5 hours, 7.5 hours, 10 hours, 12 hours, 24 hours.In some embodiments, sample quilt Exposed to 800 luxs from fluorescence light source or at least 5mW/cm2 from blue led.

Skilled addressee will appreciate that judge heterogeneous material whether the method for antibacterial (dark).In a kind of embodiment In, antibacterial exposure causes to reduce at least 10% (residue 90%), at least 50% (residue 50%), at least 99% (remaining at least 1%), at least 99.9% (residue at least 0.1%) or at least 100% (residue 0%).Determine heterogeneous material whether antibacterial (dark) An example can the amount of bacterium be present by assessing；For example, make heterogeneous material in the case where being not exposed to visible ray After material contacts with bacterium, the reduction or reduction of the number of bacterium colony be present.

Skilled addressee will appreciate that judge the whether antiviral method of heterogeneous material.Determining heterogeneous material is A no antiviral example can be the suppression or reduction by assessing the number of for example viral (bacteriophage) bacterium colony.In one kind In embodiment, whether antiviral measure heterogeneous material can be passed through：After heterogeneous material, with the time to depositing Counted in the number of viral bacterium colony.In one embodiment, antiviral exposure causes to reduce at least 10% (residue , at least 50% 90%) (residue 50%), at least 99% (residue at least 1%), at least 99.9% (residue at least 0.1%) or extremely Few 100% (residue 0%).

Skilled addressee will appreciate that judge heterogeneous material whether the method for decomposing volatile organic compound.Survey Determining heterogeneous material, whether an example of decomposing volatile organic compound can be by assessing organic compound in electromagnetism Radiate the degraded under (for example, visible ray).In one embodiment, a kind of optional of degrading volatile organic compounds is determined Selection method is the measure acetaldehyde degradation in the form of the reduction of incipient degradation or %；For example, with the time in the range of 0%-90%； Or in a certain amount of visible ray (for example, having 270mW/cm²The 455nm of power blue light-emitting LED) under from 3 to 10 hour Or 5 hours.In some embodiments, after heterogeneous material, be degraded to the primary quantity of acetaldehyde at least 50%, 60%th, 70%, 80%, 90% or 100%.

Skilled addressee will appreciate that judge the method whether heterogeneous material makes food additives or dyestuff fade. The example whether measure heterogeneous material allows food additives or dyestuff fade is by food dye additive Reduction or percentage of the primary quantity with the time.In one embodiment, food additives can be that natural cyanine vegetable food adds Add agent dyestuff or FDC food additives dyestuffs.In some embodiments, with 45mW/cm²Power is launched in 455nm Blue led after lower 5 hours, the colour fading of food dye additive can be 0%-60%.In some embodiments, exposure After heterogeneous material, be degraded to the primary quantity of natural cyanine vegetable food additive dyestuff at least 25%, 30%, 40%, 50%, and/or 60%.

Skilled addressee will appreciate that judge heterogeneous material whether with the active method of time maintenance；It is for example, non- The persistence of homogeneous material.In some embodiments, with 45mW/cm²5 under the blue led launched in 455nm of power After hour, the colour fading of food dye additive reduces 0%-60%.For example, in some embodiments, exposed to 85% After relative humidity and 85 DEG C continue at least 7 days, antibacterial activity is retained.

Exemplary but non-limiting embodiment is as described below：

The heterogeneous material of embodiment 1., it is included：

P-type semiconductor, it includes the first metal-oxide compound and the second metal-oxide compound, wherein described One metal-oxide compound and second metal-oxide compound have the different oxidation state of same metal, and wherein p Type semiconductor has p-type valence band；With

N-type semiconductor, it has n-type valence band more deeper than p-type valence band, wherein the n-type semiconductor is partly led with the p-type Body is in ionic charge connection.

Heterogeneous material described in the embodiment 1 of embodiment 2., it also includes noble metal, the noble metal and described the One metal-oxide compound is in ionic charge with second metal-oxide compound and connected.

Heterogeneous material described in the embodiment 2 of embodiment 3., wherein the noble metal is rhodium, ruthenium, palladium, silver, osmium, platinum Or gold.

Heterogeneous material described in the embodiment 2 or 3 of embodiment 4., partly leads wherein the noble metal is loaded on n-type On body.

Heterogeneous material described in the embodiment 1,2,3 or 4 of embodiment 5., it also includes the second n-type semiconductor, wherein At least a portion of second n-type semiconductor separates with the p-type semiconductor ionic charge.

Heterogeneous material described in the embodiment 5 of embodiment 6., wherein second n-type semiconductor aoxidizes comprising cerium Thing.

Heterogeneous material described in the embodiment 6 of embodiment 7., wherein the cerium oxide is CeO₂。

Heterogeneous material described in the embodiment 5 of embodiment 8., wherein second n-type semiconductor includes multiphase TiO₂。

Heterogeneous material described in the embodiment 1,2,3,4,5,6,7 or 8 of embodiment 9., wherein first metal oxygen Compound compound includes copper (I) and second metal-oxide compound includes copper (II), first metal oxide Compound includes cobalt (II) and second metal-oxide compound includes cobalt (III), first metal-oxide compound Mn (III) is included comprising Mn (II) and second metal-oxide compound, first metal-oxide compound includes Fe (II) and second metal-oxide compound include Fe (III), or, first metal-oxide compound includes Ir (III) and second metal-oxide compound includes Ir (IV).

Heterogeneous material described in the embodiment 1,2,3,4,5,6,7,8 or 9 of embodiment 10., wherein the p-type is partly led Body is loaded in the n-type semiconductor.

Heterogeneous material described in the embodiment 1,2,3,4,5,6,7,8 or 9 of embodiment 11., wherein the p-type is partly led Body is substantially dispersed in the n-type semiconductor.

Heterogeneous material described in the embodiment 1,2,3,4,5,6,7,8,9,10 or 11 of embodiment 12., wherein the p The form of type semiconductor is the particle with 100nm or smaller particle diameter.

Heterogeneous material described in the embodiment 9 of embodiment 13., wherein the p-type semiconductor includes copper (I) and copper (II)。

Heterogeneous material described in the embodiment 13 of embodiment 14., wherein the p-type semiconductor includes Cu_xO。

Heterogeneous material described in the embodiment 14 of embodiment 15., wherein the Cu_xO valency is chemically to control System.

Heterogeneous material described in the embodiment 9 of embodiment 16., wherein copper (I)：The ratio of copper (II) is 10:90 arrive 30:Between 70.

It is non-equal described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 or 16 of embodiment 17. Material, wherein the p-type semiconductor is the 0.001-10 weight % of heterogeneous material and the n-type semiconductor is heterogeneous material The 90-99.999 weight % of material.

It is non-described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 or 17 of embodiment 18. Homogeneous material, wherein the n-type semiconductor is the oxide of tungsten, tantalum, tin, zinc, strontium, zirconium, barium, indium, aluminium or cerium.

It is non-described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 or 17 of embodiment 19. Homogeneous material, wherein the n-type semiconductor includes Sn-Ti (O, C, N)₂、MgTi₂O₅、CeO₂、KTaO₃、Ta₂O₅、SnO₂、WO₃、 ZnO、SrTiO₃、BaTiO₃、ZrTiO₄、In₂TiO₅、Al₂TiO₅Or LiCa₂Zn₂V₃O₁₂。

It is non-described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 or 17 of embodiment 20. Homogeneous material, wherein the n-type semiconductor is Al_2-xIn_xTiO₅, wherein 0<x<2.

It is non-described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 or 17 of embodiment 21. Homogeneous material, wherein the n-type semiconductor is Zr_1-yCe_yTiO₄, wherein 0<y<1.

It is non-described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 or 17 of embodiment 22. Homogeneous material, wherein the n-type semiconductor is titanium oxide, the titanium oxide has by adulterating controlled valence band.

It is non-described in the embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16 or 17 of embodiment 23. Homogeneous material, wherein the n-type semiconductor is doping N, C or the titanium oxide of the two.

Heterogeneous material described in the embodiment 22 of embodiment 24., wherein the n-type semiconductor is titanium oxide, institute Titanium oxide is stated to include by formula (Ti_1-rM_r)(O_2-s-tC_sN_t) represent compound, wherein：

M is Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn or Cu or combinations thereof；

R is 0-0.25；

S is 0.001-0.1；And

T is 0.001-0.1.

Heterogeneous material described in the embodiment 24 of embodiment 25., it includes (Ti_0.99Sn_0.01)(O_2-s-tC_sN_t)、 (Ti_0.97Sn_0.03)(O_2-s-tC_sN_t)、(Ti_0.95Sn_0.05)(O_2-s-tC_sN_t)、(Ti_0.90Sn_0.10)(O_2-s-tC_sN_t)、(Ti_0.85Sn_0.15) (O_2-s-tC_sN_t)、(Ti_0.985Ni_0.015)(O_2-s-tC_sN_t)、(Ti_0.98Ni_0.02)(O_2-s-tC_sN_t)、(Ti_0.97Ni_0.03)(O_2-s- _tCsNt)、(Ti_0.99Sr_0.01)(O_2-s-tCsNt)、(Ti_0.97Sr_0.03)(O_2-s-tCsNt)、(Ti_0.95Sr_0.05)(O_2-s-tC_sN_t)、 (Ti_0.97Ba_0.03)(O_2-s-tC_sN_t)、(Ti_0.95Ba_0.05)(O_2-s-tC_sN_t)、(Ti_0.94Sn_0.05Fe_0.01)(O_2-s-tC_sN_t)、 (Ti_0.94Sn_0.05Ni_0.01)(O_2-s-tC_sN_t)、(Ti_0.99Fe_0.01)(O_2-s-tC_sN_t)、(Ti_0.95Zn_0.05)(O_2-s-tC_sN_t)、 (Ti_0.77Sn_0.15Cu_0.08)(O_2-s-tC_sN_t)、(Ti_0.85Zn_0.15)(O_2-s-tC_sN_t)、(Ti_0.90Bi_0.10)(O_2-s-tC_sN_t)、 (Ti_0.996V_0.004)(O_2-s-tCsNt)、(Ti_0.984V_0.016)(O_2-s-tCsNt)、(Ti_0.970V_0.03)(O_2-s-tCsNt)、 (Ti_0.997Mo_0.003)(O_2-s-tC_sN_t)、(Ti_0.984Mo_0.016)(O_2-s-tC_sN_t)、(Ti_0.957Mo_0.043)(O_2-s-tC_sN_t)、 (Ti_0.97W_0.03)(O_2-s-tC_sN_t)、(Ti_0.95W_0.05)(O_2-s-tC_sN_t)、(Ti_0.996V_0.004)(O_2-s-tC_sN_t)、(Ti_0.984V_0.016) (O_2-s-tC_sN_t) or (Ti_0.970V_0.03)(O_2-s-tC_sN_t)。

Heterogeneous material described in the embodiment 16 of embodiment 26., wherein the n-type semiconductor includes (Ti_1-rM_r) (O_2-s-tC_sN_t), wherein：

M is Sn；

R is 0-0.25；

S is 0.001-0.1；And

T is 0.001-0.1.

Heterogeneous material described in the embodiment 26 of embodiment 27., wherein r are more than 0.

Heterogeneous material described in the embodiment 26 of embodiment 28., wherein r is 0, and the semiconductor includes rutile Phase and Anatase.

Heterogeneous material described in the embodiment 16 of embodiment 29., wherein the n-type semiconductor is tin-oxide.

The method of the chemical decomposition compound of embodiment 30., methods described include：In the presence of light, make described chemicalization Compound is exposed to photochemical catalyst, and the photochemical catalyst includes the homogeneous material any one of embodiment 1-29.

Method described in the embodiment 30 of embodiment 31., wherein the chemical compound is pollutant.

The method that embodiment 32. kills microorganism, methods described include：In the presence of light, the microbial exposure is made In photochemical catalyst, the photochemical catalyst includes the homogeneous material any one of embodiment 1-29.

Embodiment

I. synthesize

Embodiment 1 (a) synthesis n-type semiconductors (Ex-1)

Ti(CNO)₂:Sn(Ex-1)：By 3.78g tin (II) 2 ethyl hexanoic acid salt [also known as tin (II) caprylate and/or octanoic acid Stannous] (Spectrum Chemicals, Gardena, CA, the U.S.), double (ammonium lactate) dihydros of the weight % of 30ml 50 titanium (IV) Oxide (lactic acid titanium, [Tyzor LA]) (Sigma Aldrich, St.Louis, MO, the U.S.) solution and 15.0g ammonium nitrate (NH₄NO₃) (Sigma Aldrich, St.Louis, MO, the U.S.) be dissolved in 25ml counter-infiltrations (RO) purified water, then heat To 150 DEG C and stir 20 minutes.Then under ambiance (internal ambience) and pressure condition, caused mixture is being preheated Muffle furnace in heated 40 minutes at 350 DEG C.Caused powder is placed in the Muffle furnace of preheating, then in environmental condition Under at 475 DEG C annealing continue 40 minutes.

Embodiment 1 (b) is loaded

In a water bath at 90 DEG C, by the Ti (O, C, N) of conbustion synthesis₂:Sn (6g) mixes lasting 3 with 6M HCl (60mL) Hour, stir simultaneously.Then mixture is cooled to room temperature, filtered by 0.2 micron of film filter paper, with 100-150mL go from Sub (DI) water washing, is finally dried overnight lasting 10-15 hours at room temperature.

Copper is relative to processed Ti (O, C, N)₂:Sn (1g) weight fraction is 0.01.By 10mLCuCl₂.2H₂O The aqueous solution of (26.8mg) and Ti (O, C, N) processed 1g₂:Sn is stirred 1 hour at 90 DEG C.1.5ml is contained into NaOH The aqueous solution of (50mg) and glucose (250mg) is added in 90 DEG C of reactant mixture, is stirred simultaneously.Add glucose and After NaOH aqueous solution, stirring mixture continues other 1 hour, is subsequently cooled to room temperature, then passes through 0.2 micron of film Filter paper filters, and with 100-150mL DI water washings, is finally dried overnight in an oven at 110 DEG C (10-15 hours).

CuO in Ex-1:Cu₂O part by weight is measured as 0.789:0.211.By contrast, according to Qui et al., ACS The CuxO/TiO that Nano, 6,1609-1618 are obtained₂The CuO of nano composite material:Cu₂O part by weight is 0.169:0.831.

Embodiment 1 (b) ' comparative examples 0 (CE-0)

In 5-10mL methanol, using mortar and pestle, the CuO with hand by Cu total weight percent for 0.25 weight % + 0.125 weight % Cu₂O and Sn-Ti (OCN)₂Photochemical catalyst physical mixed.Lasting mixing is until all methanol have evaporated.

Embodiment 1 (c) comparative examples 1 (CE-1)

To prepare CE-1 (Ti (CNO) similar to the method for embodiment 1 (a)₂:Sn), except：Not loaded Cu_xO (only steps A), so as to producing unsupported Ti (CNO)₂:Sn (no Cu_xO)。

Embodiment 1 (d) comparative examples 2 (Ex-1A)

To prepare Ex-1A similar to the method for above-described embodiment 1 (b), except：50mg NaOH are replaced using 25mgNaOH And replace 250mg glucose using 125mg glucose.

Embodiment 1 (d) ' comparative examples 2 ' (Ex-1B)

To prepare Ex-1B similar to the method for above-described embodiment 1 (b), except：Copper relative to processing Ti (O, C, N)₂: Sn (1g) weight fraction is 0.005.

Embodiment 1 (e) comparative examples 3 (Ex-2 and Ex-3)

To prepare Ex-2 (plasma WO similar to above-mentioned Ex-1 method₃) and Ex-3 (business GTP WO₃), except：Make With the plasma WO of same molar₃Or business GTP WO₃Instead of Ti (O, C, N)₂:Sn photochemical catalysts；Not to reactant mixture Middle addition NaOH, and replace 250mg glucose using 125mg glucose.With the United States Patent (USP) Shen submitted with January 10th, 2013 Please the similar method of method described in 13/738,243 prepare plasma WO₃, religion of the patent application on identical content Reference was turned on to be incorporated herein.GTP WO₃Purchased from Global Tungsten＆Powder (Towanda, PA, the U.S.) and unfavorable Used with extra purifying or annealing.

1 mole of double (ethylenediamine) copper (II) hydroxide solutions of 0.159mL are mixed with 10mL RO water, and with 1gWO₃Stirred 1 hour at 90 DEG C.Then, glucose (125mg) is added into 90 DEG C of reactant mixture, is stirred simultaneously.Add After the aqueous solution for entering glucose, stirring mixture continues other 1 hour, is subsequently cooled to room temperature, then passes through 0.2 micron Film filter paper filtering, with 100-150mL DI water washings, be finally dried overnight in an oven at 110 DEG C (10-15 hours).

Embodiment 1 (f) comparative examples 4 (Ex-4, Ex-5, Ex-6, CE-2)

To prepare Ex-4, Ex-5, Ex-6 and CE-2 similar to Ex-1 method, except：Use the CeO of same molar₂ Instead of Ti (O, C, N)₂:Sn.In addition, loading condition is changed as described below：Ex-4：NaOH (25mg) and glucose (125mg) Aqueous solution；Ex-5：Without glucose；Ex-6：Concentration/concentration of glucose (62.5mg) and NaOH (25mg).

CE-2 is similar to CE-1, except：CE-2 is unsupported mole equivalent (relative to Ti (O, C, N)₂:Sn CeO)₂ (Sigma Aldrich, St.Louis, MO, the U.S.).CeO₂It is used without when such as being received from supplier and carries out extra purifying Or annealing.

Embodiment 1 (g) comparative examples 5 (Ex-7, CE-3)

To prepare Ex-7 similar to above-mentioned Ex-1 method, except：Using the insulator of same molar, Al is used₂O₃Generation For Ti (O, C, N)₂:Sn, using 25mg NaOH, and use 125mg glucose.Relative to Al₂O₃, Cu_xO loads are 1 weight % Cu.CE-3 is similar to CE-1, except：CE-3 is unsupported mole equivalent (relative to Ti (O, C, N)₂:Sn Al)₂O₃。 Al₂O₃It is used without when such as being received from supplier and carries out extra purifying or annealing.

Embodiment 1 (h) comparative examples 6 (Ex-8, CE-4)

To prepare Ex-8 similar to above-mentioned Ex-1 method, except：Use the n-type UV active photocatalysts of same molar Agent, use Ta₂O₅Instead of Ti (O, C, N)₂:Sn, use 25mg NaOH and 125mg glucose.Relative to Ta₂O₅, Cu_xO is loaded 1 weight % Cu.CE-4 is similar to CE-1, except：CE-4 is unsupported mole equivalent (relative to Ti (O, C, N)₂:Sn) Ta₂O₅。Ta₂O₅It is used without when such as being received from supplier and carries out extra purifying or annealing.

Embodiment 1 (i) comparative examples 7 (Ex-9, Ex-10, Ex-11, Ex-19, Ex-20, CE-4A)

To prepare Ex-9 similar to above-mentioned Ex-1 method, except：Use the n-type UV active photocatalysts of same molar Agent, use SnO₂Instead of Ti (O, C, N)₂:Sn.Relative to SnO₂, Cu_xThe Cu that O loads are 1 weight %.The SnO of nano-scale₂(US Research Nanomaterial, Houston, TX, the U.S.) it is annealed persistently at 900 DEG C in atmosphere in batch-type furnace 1 hour.Then, it is immersed in as in the 6M HCl/water solution in Ex-1.In Ex-10, NaOH amount is 25mg and Portugal The amount of grape sugar is 125mg.In Ex-11, NaOH amount is 75mg and the amount of glucose is 375mg.In Ex-19 and Ex-20, The SnO of annealing₂It is not soaked in as in the 6MHCl aqueous solutions in Ex-1, Ex-10, Ex-11.In Ex-19, NaOH amount It is 3mg for 25mg and the glucose amount that uses.In Ex-20, NaOH amount is 25mg and the amount of glucose is 10mg.CE-4A Similar to CE-1, except：CE-4A is unsupported mole equivalent (relative to Ti (O, C, N)₂:Sn SnO)₂.Utilize not same amount NaOH and glucose simultaneously load fixed amount 1 weight %Cu (relative to SnO₂), generate different main body outward appearance face Color.

Embodiment 1 (j) comparative examples 8 (Ex-12, CE-5, Ex-13)

To prepare Ex-12 similar to above-mentioned Ex-1B method.In rutile TiO₂In (Tayca, Inc.Osaka, Japan) Carry out Cu_xO is loaded, except：50mg NaOH are replaced using 25mg NaOH and replace 250mg glucose using 125mg glucose.

CE-5 is similar to CE-1, except：CE-5 is unsupported mole equivalent (relative to Ti (O, C, N)₂:Sn golden red) Stone TiO₂(Tayca, Inc.Osaka, Japan).Rutile TiO₂It is used without when such as being received from supplier and carries out additionally pure Change or anneal.

For Ex-13, by 10g business WO₃(Global Tungsten Powder, Sylvania, PA, the U.S.) is 400 Annealed 1 hour at DEG C.By [Pt (NH₃)₄]Cl₂(0.181mg Alfa Aesar, WardHill, MA, the U.S.)] it is dissolved in The WO annealed with 2.0g in 15.0mL RO water and under room temperature (RT)₃Stirring continues 2 hours together.Then, it is by aperture 0.2 micron of film filter paper filtering, with RO water washings, and is dried overnight at 120 DEG C.Material is in atmosphere 400 caused by making Annealing continues other 1 hour at DEG C.

Embodiment 1 (k) comparative examples 9 (Ex-13-17, CE-6)

To prepare Ex-14 to Ex-17 similar to the method for those described above, except：By different amounts of [Pt (NH₃)₄]Cl₂] And/or IrCl₃/IrO₂It is dissolved in 15.0mL RO water.Referring to such as table 1 below：

Table 1

CE-6 is similar to CE-1, except：CE-5 is unsupported mole equivalent (relative to Ti (O, C, N)₂:Sn WO)₃ (Global Tungsten Powder, PA, the U.S.).WO₃It is used without when such as being received from supplier and carries out extra purifying Or annealing.

Embodiment 1 (l) synthesis n-type semiconductors (Ex-18)

MgTi2O5 is synthesized：In 250mL low profile Pyrex beakers, by 2.663g Mg (NO₃)₂·6H₂O(Sigma Aldrich, St.Louis, MO, the U.S.), 5g ammonium nitrate (Sigma Aldrich, St.Louis, MO, the U.S.), 1.5g urea (Sigma Aldrich, St.Louis, MO, the U.S.) and double (ammonium lactate) hydroxide (lactic acid the titanium, [Tyzor of 10mL titaniums (IV) LA]) (Sigma Aldrich, St.Louis, MO, the U.S.) is dissolved in about 10mL DI water.Then in ambiance (Indoor Air Atmosphere) and pressure condition under, caused mixture is heated 20 minutes at 350 DEG C in the Muffle furnace of preheating.By caused powder End is placed in the Muffle furnace of preheating, and then annealing lasts about 30 minutes at 600 DEG C at ambient conditions.

Loaded Cu_xO MgTi₂O₅：With similar to the method described in embodiment 1 (b) by Cu_xO loads to MgTi₂O₅On, Except：In this preparation, HCl preparation processes are not used.Used NaOH preparation processes are similar to institute in embodiment 1 (b) State.Copper is relative to MgTi₂O₅Weight fraction be 0.01.By 10mL CuCl₂.2H₂O (26.8mg) aqueous solution and 1g MgTi₂O₅Stirred 1 hour at about 90 DEG C.Aqueous solutions of the 1.5ml containing NaOH (25mg) and glucose (125mg) is added to In about 90 DEG C of reactant mixture, stir simultaneously.Add after glucose and NaOH aqueous solution, stirring mixture continues separately Outer 1 hour, room temperature is subsequently cooled to, is then filtered by 0.05 micron of film filter paper, with 100-150mL DI water washings, finally Dried about 2 hours at 110 DEG C in an oven.

Embodiment 1 (m) (Ex-20 (load multiphase TiO₂Cu_xO))

So that multiphase n-type semiconductor is loaded into Cu similar to the method described in embodiment 1 (b)_xOn O.Copper is relative to more Phase n-type semiconductor (the Rutile Type TiO of 87% anatase TiO2/13%₂, with trade (brand) name " P25 " [EvoniK Degussa, NJ, the U.S.] sell) weight fraction be 0.01.By 15mL CuCl₂.2H₂O (26.8mg) aqueous solution and 1g P25 is stirred 1 hour at about 90 DEG C.Then, aqueous solutions of the 1.5ml containing NaOH (25mg) and glucose (125mg) is added Into about 90 DEG C of reactant mixtures, stir simultaneously.Add after glucose and NaOH aqueous solution, stirring mixture continues Other 1 hour, room temperature is subsequently cooled to, is then filtered by 0.05 micron of film filter paper, with 100-150mL DI water washings, most Dried about 2 hours at 110 DEG C in air -oven afterwards.

Embodiment 1 (n) (CE-7)

To prepare comparative example CE-7 similar to the method described in embodiment 1 (m), except：In methanol (5-10mL), use Hand is by 0.25 weight % CuO+0.125 weight % Cu₂O and 0.625 weight % P25 physical mixeds, until methanol essence Upper evaporating completely.

Embodiment 1 (o) (Ex-19 (AgVWO₆))

By 4.12g vanadyl oxalates (Stratcor, Inc, Arkansas, the U.S.), 0.3g glycine (Sigma Aldrich, St.Louis, MO, the U.S.), 0.62g ammonium nitrate (Sigma Aldrich, St.Louis, MO, the U.S.) and 1.484g ammonium metatungstates (Global Tungsten＆Powder, PA, the U.S.) is dissolved in about 5ml counter-infiltrations (RO) purified water.In 250mL beakers in low form In, 1g silver nitrates (Alfa Aesar, the U.S.) are added into the solution to obtain brown slurry, it is then, (indoor in ambiance Atmosphere) and pressure condition under, caused mixture is heated about 20 minutes in the Muffle furnace of preheating at about 350 DEG C.Will production Raw powder is placed in the Muffle furnace of preheating, and then annealing lasts about 60 minutes at 500 DEG C at ambient conditions, and this has been produced Raw yellow powder (Ex-19).

Embodiment 1 (p) (Ex-20 (AgCa₂Zn₂V₃O₁₂))

By 6.19g vanadyl oxalates (Stratcor, Inc, Arkansas, the U.S.), 1.11g glycine (Sigma Aldrich, St.Louis, MO, the U.S.), 1.75g zinc nitrates hexahydrate (SigmaAldrich, St.Louis, MO, the U.S.), 1.39g calcium nitrate tetrahydrates (Sigma Aldrich, St.Louis, MO, the U.S.), 2.49g ammonium nitrate (Sigma Aldrich, St.Louis, MO, the U.S.) it is dissolved in about 10ml counter-infiltrations (RO) purified water.In 250mL low profile glass beakers In, 0.5105g silver nitrates (Alfa Aesar, the U.S.) are added into the solution to obtain brown slurry, then, in ambiance Under (internal ambience) and pressure condition, caused mixture is heated about 20 minutes in the Muffle furnace of preheating at about 350 DEG C. Caused powder is placed in the Muffle furnace of preheating, then annealing lasts about 60 minutes at about 600 DEG C at ambient conditions, This has produced yellow powder (Ex-20).

Embodiment 1 (q) (Ex-21 (Ag₃PO₄))

In 50mL glass beakers, 5g silver nitrates (Alfa Aesar, the U.S.) are dissolved in 10ml counter-infiltrations (RO) purifying In water.In single 50mL glass beakers, by 1.128g ammonium dihydrogen phosphates (Sigma Aldrich, St.Louis, MO, U.S. State) it is dissolved in 10ml counter-infiltrations (RO) purified water.The water-based of silver nitrate is added dropwise into the aqueous solution of ammonium dihydrogen phosphate Solution, while stir ammonium dihydrogen phosphate.Finally filter the yellow mercury oxide formed during this addition at room temperature simultaneously Dried 2 hours at 110 DEG C in air -oven.

Embodiment 2：Support the sign of P- catalyst (P-cats)

Embodiment 2 (a)：Powder X-ray RD characterizes (Ex-1A, CE-1, Ex-4, CE-2, Ex-7 and CE-3)

Using Cu K- α radiation (Rigaku Miniflex II [Rigaku Americas, Woodland, TX, the U.S.), With 1 °/minute, Powder x-ray diffraction analysis Ex-1A, CE-1, Ex-4, CE-2, Ex-7 and CE-3 powder sample is utilized.Ex- 1 and CE-1 X-ray diffraction analysis result is shown in Fig. 3, and which confirms anatase TiO₂Presence.By XRD spectrum (figure 3) it is able to verify that：Ti(O,C,N)2:Sn Anatase is retained, even if loaded Cu_xAlso in this way, because caused XRD after O The powder diffraction standard card that the joint of collection of illustrative plates and joint committee (Newton Square, PA, the U.S.) is formulated No.00-021-1272 anatases-TiO2] (JCPDS) comparison show the peak substantially the same with Anatase collection of illustrative plates (should Phase material generally has visible light photocatalysis active).

In addition, to analyze Ex-4 and Ex-7 powder sample similar to above-mentioned Ex-1A method, except：Rubbed using identical Your Ex-4 and Ex-7 of amount replace Ex-1A.Using Cu K- α radiation (Rigaku Miniflex II [Rigaku Americas, Woodland, TX, the U.S.), with 1 °/minute, using Powder x-ray diffraction, as a result it is shown in Figure 4 and 5.Figure 4 and 5 Shown in X-ray diffraction result confirm, Cu_xO loads do not influence the main semiconductor phase of various n-type materials substantially.

Embodiment 2 (b)：DRS is characterized

Utilize the spectrometry that diffuses (DRS) analysis Ex-1A, CE-1 (Fig. 6)；Ex-4 and CE-2 (Fig. 7), Ex-7 and CE-3 The powder sample of (Fig. 8).As a result it is shown in Fig. 6,7 and 8, it shows：At least tin dope thing (Ex-1A), CeO₂(Ex-4) and Al₂O₃(Ex-7) absorption improved in visible spectrum (400nm-800nm) is shown, and CE-1, CE-2 and CE-3 are then not So.Therefore, because Anatase and in XRD spectrum and visible absorption observe anatase TiO₂Confirm Ti (O, C, N)₂:Sn、CeO₂And Al₂O₃It is supported in matrix.The Cu of load_xLonger wavelength sides of the O on the ABSORPTION EDGE edge of semiconductor, which has, inhales Receive；And the if Cu of load_xO contains CuO and Cu₂O mixture, then except the Cu of load_x, will also observation outside O absorption To their characteristic absorption respectively between 600nm-800nm between 500nm-600nm.

3. light-catalysed Setup Experiments of embodiment (Ex-1A and CE-1)

Ex-1A (130mg) is prepared according to the method for the foregoing description in the disclosure, is added into 1.04ml DI water to produce The coating solution of 10 weight % solid materials in unboiled water.Caused dispersion is homogenized using ultrasonic homogenizer.Use rotation Coating machine (1200rpm/40 seconds), utilize obtained product coated glass substrates (50mm × 75mm).Warp is heated at 120 DEG C The base material of coating.Another (slide) is prepared in the same way, except：Ex-1A is replaced using CE-1 (130mg).

Under the full spectral radiance of Xe (xenon) lamp (lamp power output is 300W), heating will rotation at 120 DEG C on hot plate The sheet glass for turning coating continues 1 hour.Then it will be sealed in per a piece of in single 5L vacuum Tedlar bags, and then inject 3L rings The acetaldehyde of border air and 80mL 3500ppm.Each bag is gently massaged with hand 2 minutes, then place it in dark place and continue 15 points Clock, the acetaldehyde concentration estimated by gas chromatography-flame ionization detector (GC-FID) is 80 ± 2ppm.Sample will be contained Each Tedlar bags put back to dark place and continue 1 hour.Being exposed to piece/Tedlar bags has 270mW/cm²Luminous intensity 455nm array blue led.Sample is collected in every 30 minutes by GC-FID automatic injection mouth, and between subsequent 30 minutes Every the amount of the middle remaining acetaldehyde of estimation.Fig. 9 chart illustrates Ex-1A VOC performance datas.Chart is shown：In general, with it is naked The Ti (CNO) of dew₂:Sn (CE-1) is compared, when by Ti (CNO)₂:Sn and Cu_xWhen O is combined (Ex-1A), performance is improved.

The antibacterial experiment of embodiment 4.

Embodiment 4A.

Base material (1 " × 2 " glass plates) is prepared as described below：The continuous IPA (isopropanol) for applying 70% and 100% second Alcohol (EtOH), is then dried in atmosphere.Ex-1B is dispersed in 100%EtOH with 2mg/mL concentration, then by 100 μ L Suspension is applied on base material, is then dried.Application process is repeated 5 times to obtain 1mg Ex-1B on base material.Then in room temperature Lower dry substrate.Coated base material is placed in the glass dish containing the filter paper being soaked in water to maintain humidity, and will Glass liner is inserted between base material and filter paper to separate them.

By E.coli (ATCC 8739) in LB containing 20ml (lysogeny fluid nutrient medium/luria fluid nutrient mediums) agar A diameter of 10cm Petri dish on rule, and be incubated overnight at 37 DEG C.For each experiment, the inoculation of picking single bacterium colony Into 3mL Nutrient broths, then the culture after inoculation is incubated to 16 hours at 37 DEG C to produce overnight culture (~109 cells/mL).The fresh logarithmic phase culture as described below for obtaining overnight culture：Overnight culture is diluted 100 Times, it is then seeded into the 5cm Petri dish of another agar containing LB and is incubated 2.5 hours at 37 DEG C.With 0.85% Fresh cultured thing is diluted 50 times by salt solution, so as to produce 2 × 10⁶Cell/mL cell supernates.It is thin that 50 μ L are drawn with pipettor Born of the same parents' suspension is added on the glass baseplate of each deposition.By sterile (in 70%EtOH, then in 100%EtOH) plastics Film (20mm × 40mm) is placed on suspension with dispersed below film.Sample is kept into (Cu in the dark_xO₂- dark) probable Afterwards in blue LED light (455nm, 10mW/cm2) (CuO₂- light) under radiate.At selected time point, for example, 30 minutes/60 The increment of minute, sample is placed in 10mL 0.85% salt solution and is vortexed with eluting bacterial.Retain the suspension of elution Thing, then using 0.85% salt solution serial dilution, be then coated on LB agar and be incubated overnight at 37 DEG C to determine work Cell number (in terms of CFU/ samples).

As a result it is shown in Figure 10 and 11.In view of this：Due to the presence of flexible (flexible) copper ion, even in Dark place can also be observed that E-coli kills performance in 30 minutes.

Figure 10 is also shown：By Cu¹⁺It is supported on CeO₂After upper, in the dark in 1 hour and the 10mW/cm2 in 455nm light Cu is observed under blue led¹⁺E-coli performance is killed completely.Therefore, loaded Cu_xO CeO₂It is to be used to kill E-coli Good function material.

Embodiment 4B

Ex-1 powder is prepared as described in example 1 above.Then powder is kept in the dark, in 85% relative humidity and 85 DEG C Continue 7 days.Then piece is prepared and to examine antibacterial activity similar to the method described in embodiment 4A.As a result Figure 12 A are shown in In.As a result show：After relative humidity if exposed to 85% and 85 DEG C continue 7 days, Ex-1 shows the photocatalysis of reservation Activity.

Embodiment 4C

Ex-7 is prepared as described above.Then powder is kept in the dark, continuing 20 minutes at 300 DEG C.Then piece is prepared And to examine antibacterial activity similar to the method described in embodiment 4A.As a result it is shown in Figure 12 B.As a result show：It is even if sudden and violent Be exposed to 300 DEG C continue 20 minutes after, Ex-7 retain photocatalytic activity.

Embodiment 5. is used for the photocatalysis experiment of dyestuff colour fading research

Embodiment 5A.

By measurement be used as natural blue powder food additives dyestuff (natural blue powder, ColorMaker, Anaheim, California, the U.S.) degraded compare Ex-1, CE-1 and load or unsupported Cu_xO rutile TiO2's Photocatalysis performance, 2.85g natural blue powder is dissolved in 100mLRO water, so as to produce blue powder liquid storage.By 150mg Every kind of sample, which is placed in the 3mL blue powder liquid storages of RO water (27mL) and natural blue, continues 1 hour (without any light), then makes It is exposed to diode (455nm, the 45mW/cm of blue light-emitting²) continue 5 hours.At 1 hour, 3 hours and 5 hours, purple is utilized Outside-visible absorption spectra (Cary-50, Spectrophotometer AgilentTechnologies, Santa Clara, CA, The U.S.) concentration of blue solution produced by monitoring, so as to measure its degraded.Concentration is calculated as the intensity at 600nm peak.Knot Fruit is shown in Figure 13.Table 2 below compares the final degradation results of four kinds of catalysis materials.

Table 2：The comparison of the final dyestuff fade results of four kinds of different photochemical catalysts

By measurement be used as natural blue powder food additives dyestuff (natural blue powder, ColorMaker, Anaheim, California, the U.S.) degraded detect Ex-18 (loaded Cus_xO MgTi2O5) photocatalysis performance.With class It is similar to the method detection degraded described in embodiment 5A.As a result it is shown in Figure 17.

The photocatalysis that embodiment 6A. is used for antibacterial research is tested

The every kind of powdered samples (above-described embodiment 14-18) of 130mg are dissolved in minimal amount of RO water (about 15mL) simultaneously Homogenizing 5 minutes.

With the clean Petri dish of ethanol and hold the internal surface ion of culture dish using plasma device Continuous 1-2 minutes.The sample of every kind of compound of homogeneous is poured into the Petri dish through processing, then heated at 120 DEG C Being uniformly distributed when turn simultaneously is to improve sample drying.After sample drying, Petri dish is placed under UV lamp (300W) Continue 1 hour.Then each Petri dish is sealed in single 5L vacuum Tedlar bags, then injects 3L surrounding airs With 80mL3500ppm acetaldehyde.Each bag is gently massaged with hand 2 minutes, then place it in dark place and continue 15 minutes.Pass through The acetaldehyde concentration of gas chromatography-flame ionization detector (GC-FID) estimation is 80 ± 2ppm.The each of sample will be contained Tedlar bags put back to dark place and continue 1 hour.Being exposed to piece/Tedlar bags has 0.656mW/cm²Luminous intensity 455nm Array blue led.Sample is collected for every 30 minutes by GC-FID automatic injection mouth, and estimated in 30 minutes subsequent intervals The amount of remaining acetaldehyde.As a result it is shown in table 3 below.

Table 3

Figure 14, which is shown, utilizes WO₃(business GTP) (CE-6), the WO for loading 0.05 mole of %Pt₃(Ex-13) 0.1, is loaded Mole %IrO₂WO₃(Ex-16) and load 0.05 mole of %Pt and 0.1 mole of both %IrO2 WO₃(2 times) (Ex-17) Acetal dehyde decomposition rate (Ct/Co).Quite entertaining, it is observed that following result：Supporting Pt is to the blueness in 455nm LED(0.656mW/cm²) under acetaldehyde degradation have positive effect, and load independent IrO₂WO₃To the blue led in 455nm (0.656mW/cm²) under acetaldehyde degradation do not influence.However, under the same conditions, when with single Pt (0.05 mole of %) Or single IrO₂(0.1 mole of %) or individually exposed GTP WO₃Compared to when, supporting Pt (0.05 mole of %) and IrO₂(0.1 Mole %) WO of the two₃The light degradation of acetaldehyde is caused to further enhance.

Embodiment 5c

By instrument additive dyestuff FD＆C Blue No.2 dyestuffs (synthesis blue powder, Chromatech, Inc, Michigan, the U.S.) degraded compare Ex-10 (SnO₂), CE-4A and single food additives dyestuff FD＆C Blue The photocatalysis performance of No.2 dyestuffs (blue No. two dyestuffs).G natural blue powder is dissolved in 100mL RO water, so as to produce Blue powder liquid storage.Place the every kind of samples of 150mg.To determine photocatalysis performance similar to the method described in embodiment 5a.Knot Fruit is shown in Figure 15.

By instrument additive dyestuff FD＆C Blue No.2 dyestuffs (synthesis blue powder, Chromatech, Inc, Michigan, the U.S.) degraded compare Ex-18 (MgTiO₅) and loaded Cu_xO Ex-1 (SnTi (OCN)₂) photocatalytic Energy.2.85g natural blue powder is dissolved in 100mL RO water, so as to produce blue powder liquid storage.Place the every kind of samples of 150mg Product.To determine photocatalysis performance similar to the method described in embodiment 5a.As a result it is shown in Figure 16.

Embodiment 6：E.coli (ATCC 8739) photocatalysis inactivation

6A methods：

Base material (1 " × 2 " glass plates) is prepared as described below：The continuous IPA (isopropanol) for applying 70% and 100% second Alcohol (EtOH), is then dried in atmosphere.Ex-1B is dispersed in 100%EtOH with 2mg/mL concentration, then will about 100 μ L suspensions are applied on base material, are then dried.Application process is repeated 5 times to obtain 1mg Ex-1B on base material.Then in room The lower dry substrate of temperature.Coated base material is placed on to maintain humidity in the glass dish containing the filter paper being soaked in water, and Glass liner is inserted between base material and filter paper to separate them.

E.coli (ATCC 8739) is rule on a diameter of 5cm of the LB agar containing about 25ml Petri dish, and It is incubated overnight at about 37 DEG C.For each experiment, picking single bacterium colony is inoculated into about 3mL Nutrient broths, then will Culture after inoculation is incubated about 16 hours to produce overnight culture (~10 at about 37 DEG C⁹Cell/mL).Obtain as described below Obtain the fresh logarithmic phase culture of overnight culture：Overnight culture is diluted 100 times, is then seeded into another agar containing LB 5cm Petri dish in and be incubated about 2.5 hours at about 37 DEG C.Fresh cultured thing is diluted 50 times, so as to produce about 2 × 10⁶Cell/mL cell supernates.50 μ L cell supernates are drawn with pipettor to be added on each glass baseplate.Will be sterile (in 70%EtOH, then in 100%EtOH) plastic foil (20mm × 40mm) is placed on suspension with equal below film It is even scattered.At selected time point, for example, the increment of about 30 minutes, sample is placed in 10mL 0.85% salt solution simultaneously About 1 minute is vortexed under 3200rpm with eluting bacterial.The suspension eluted using 0.85% salt solution serial dilution, then apply Cloth is incubated overnight to determine number of viable cells on LB agar and at about 37 DEG C (in terms of CFU/ samples).Check by visual observation into Row counts and is multiplied by result with dilution factor to reach the number of measure.Then radiation sample, it is placed on turning blue for 455nm Under light LED with to sample provide about 45mw/cm².As a result it is shown in Figure 19.

CE-7 and Ex-7A anti-microbial property is determined as described in embodiment 6A, except：Using molar equivalent CE-7 and Ex-7A replaces Ex-1B.As a result it is shown in Figure 17 (CE-7) and 18 (Ex-7A).

As described in embodiment 6A, compare Ex-1 (load 1%Cu by measuring antibacterial activity_xO/Sn:Ti(OCN)₂)、 Only Cu_xO and unsupported Sn:Ti(OCN)₂The anti-microbial property of (as described in embodiment 1 (a)).As a result it is shown in Figure 20.

PcatI function

By 50mg Cu_xO/P25 (produced by such as embodiment 1 (the m)) and bleaching agent (Clorox of 1mL 10% Germincidal, based on NaClO) mixed in 1.6mL Eppendorf centrifuge tubes, then it is incubated 2 under room temperature (~24C) Hour, while shake and (set 9 on the VWR of simulation is vortexed).After incubation, the micro centrifuges of Eppendorf 5430 ( Lower 2 minutes of 14167rcf) in centrifuge tube, afterwards, particle bottom of the tube formed solid precipitation thing.Carefully remove limpid supernatant Liquid, then add 1mL DI water.Vortex tube is until sediment is completely destroyed and suspension becomes homogeneous.Then centrifuge again. Repeat the process 4 times.

After last time centrifuges, sediment is set to be again suspended in 1mL DI water, and it is with cover in 20mL with 4mL DI water Clear glass bottle in mix.5mL methanol is added, so that the cumulative volume in bottle reaches~10mL.

Magnetic stirring bar (1/2 " × 1/8 ", disposable) is added in bottle, is then placed within agitating plate (1000rpm) On.A300W xenon lamps (Oriel 68811) are placed in place of small bottle wall about 15cm.It is small that radiation continues 1 in vent hood When, and the temperature change during process in bottle can be neglected.

After radiation, the content in bottle is centrifuged to remove all liq.Sediment is dried in a vacuum, and in 25mL It is resuspended in 200 normal intensities (proof) ethanol.Then mixture is ultrasonically treated in ultrasonoscope and continues 20 minutes.

On the side for making the sheet glass that 100 microlitres of sonicated dispersion homogeneous are dispersed in 1 " × 2 ".Dry tack free After (in vent hood), the process is repeated, continues totally 5 layers of coating.Then coated piece is used for our normal bacterial In experiment.

In order to compare, 50mg Cu are handled in the same way as described above_xO/Al₂O₃, coated piece is then manufactured with it. These to photo with Cu_xO/P25 identical methods are subjected to normal bacterial experiment.Draw from the result secretly tested.

As shown in Figure 22 (left figure), fresh Cu_xO/P25 (1) shows high activity, makes in the dark in 30 minutes E.coli reduces by 3 log units.The material (2) handled through bleaching agent shows the activity reduced much, in the dark after 2 hours Only realize that 3 logarithms are reduced.Material is once bleached agent processing, just with xenon lamp radiation, however, caused result (3) is shown Go out the activity for being comparable to unprocessed sample (1), also realized that 3 logarithms are reduced in 30 minutes.

By contrast, in Cu_xO/Al₂O₃In the case of (Figure 22, right figure), do not observe it is this by radiation recapture function, Because the sample (3) for handling/radiating through bleaching agent shows similar to the sample (2) only handled through bleaching agent but is substantially less than The activity of fresh sample (1).

PcatII function

In order to study how the duration of bleaching agent processing influences to load the activity of the material of Cu oxide, setting is utilized The duration is handled for the bleaching agents of 2 hours and 16 hours to implement above-mentioned experiment.All other aspect of experiment remains identical. From these result will be reduced through handling sample with the logarithm from unprocessed material

In Figure 23 left figure, Cu_xO/Al₂O₃Bleaching agent processing cause dark activity to significantly reduce.Experiment under light is not Can big degree ground activity recovery.By contrast, in Cu_xIn the case of O/Pcat (P25) (Figure 23, right figure), although dark active quilt Similarly influence, but photolytic activity is resumed.The key point of the experiment is：After bleaching agent is handled 16 hours, light recovers Process still largely undamaged mistake, this is Cu_xO/Pcat persistent strong evidence.

Adulterate the WO3 of boron water-based conbustion synthesis

The WO3 of the doping boron with ε phases is prepared using water-based combustion method.

By 5mg ammonium metatungstates hydrate (Inframat Advanced Materials, Manchester, CT, the U.S.), 100mg boric acid (Sigma-Aldrich, St.Louis MO, the U.S.), 2g carbohydrazides (Sigma-Aldrich) and 10g ammonium nitrate (Sigma-Aldrich) it is dissolved in 50ml DI water.Then aqueous solution is placed in Muffle furnace, is preheated to about 420 DEG C directly (lasting about 20 minutes) is burnt to essentially completing.After burning terminates, product is annealed in atmosphere at about 425 DEG C and last about 30 minutes.The body color of powder is shown as orange-yellow, and this passes through the ε WO with utilizing standard₃The powder X-ray RD spectrums of X-ray diffraction Figure (Fig. 1) (ICFF PDF card number 01-087-2404) compares and is proved.

Fig. 1：Powder X-ray RD spectrograms (right side).

Using cobalt/cobalt oxide, pass through strong, selective absorption method surface modification ε WO₃

By 1mg ε WO₃With 40.37g CoCl₂·4H₂O is dissolved in about 10mL DI water and in the bottle reaction of 40mL closings In device at about 90 DEG C stir about 2 hours.Then, the bottle reactor of closing and (thin by molecular filter is quenched in running water To 0.05 micron) filtering, with DI water washings several times (at least about 250ml) and finally at about 110 DEG C dry about 2 hours with To the ε WO of load cobalt/cobalt oxide₃。

Unless otherwise indicated, for the expression composition quantity in specification and claims, property (such as molecular weight), anti- All numerals of condition etc. are answered to be interpreted as being modified by term " about " in all cases.Therefore, in addition to indicating on the contrary, explanation Number parameter disclosed in book and appended claims is approximation, its required property that can be gone for according to the present invention And change.At least, the scope that doctrine of equivalents is applied to claims by limitation is not intended to, each number parameter at least should be by According to it is reported that effective digital digit and pass through application ordinary rounding techniques explain.

When describing present disclosure, without using should be interpreted that culvert (especially in the content of claims) during numeral-classifier compound Sheet number and plural number, it is unless otherwise indicated or otherwise clearly contradicted.Narration to this paper number ranges is merely intended to serve as To quote each stenography method (shorthand method) being individually worth for falling into the scope.Unless otherwise indicated herein, Each individually value is merged in specification, just as it is by being individually incorporated herein.Unless this otherwise noted or with Context is substantially contradicted, and all methods as described herein can be carried out in any suitable order.It is provided in this article it is any and The use of all examples or citing language (such as " such as ") is intended only to for preferably illustrating the present invention, rather than to the present invention Any claim setting limitation claimed.Language in application documents is understood not to represent that any failed call is protected The element of shield is required for the practice to the present invention.

The packet of alternative elements or embodiment disclosed herein should not be construed as limiting.Each group membership can individually be mentioned And be claimed, or other members of the group with finding herein or other elements any combination.It should be appreciated that due to it is convenient and/ Or the reason for patent, one group of one or more members can be included in one group or be deleted from the group.When any this kind of bag When including or delete generation, present specification is considered as containing the group through rewriting, to meet to used in appended claims All marlcush groups written description.

This document describes some embodiments of the present invention, including the present invention is realized most known to the present inventor Good pattern.Certainly, the change of these embodiments is would appreciate that after this area those having ordinary skill in the art reading foregoing description.This hair A person of good sense, which is expected those skilled in the art, can suitably use this kind of change, and present inventor is intended to the present invention with special with this paper Different mode applications is described surely.Therefore, at least applicable law allows, and the present invention includes institute in appended claims All modifications for the body matter stated and equivalent.In addition, it is unless otherwise indicated herein or clearly contradicted by context, in its institute It is possible in change, any combinations of said elements are as included by the present invention.

Closing, it is to be understood that embodiments disclosed herein is used merely to explain the principle of the present invention.Other workable modifications It is also within the scope of the invention.Therefore, by way of example, and not limitation, the standby of the present invention can be utilized according to teaching herein Preferred form of this.Therefore, the present invention be not limited to it is accurately shown and as described in.

Claims

1. heterogeneous material, it is included

P-type semiconductor, it includes the first metal-oxide compound and the second metal-oxide compound, wherein first gold medal Category oxide compound and second metal-oxide compound have the different oxidation state of same metal, and wherein described p Type semiconductor has p-type valence band；With

N-type semiconductor, it has n-type valence band more deeper than p-type valence band, wherein at the n-type semiconductor and the p-type semiconductor Connected in ionic charge,

Wherein, the p-type semiconductor includes copper (I) and copper (II), and the p-type semiconductor includes Cu_xO,

The n-type semiconductor includes Sn-Ti (O, C, N)₂。

2. heterogeneous material according to claim 1, it also includes noble metal, the noble metal and first metal oxygen Compound compound is in ionic charge with second metal-oxide compound and connected.

3. heterogeneous material according to claim 2, wherein the noble metal is rhodium, ruthenium, palladium, silver, osmium, platinum or gold.

4. heterogeneous material according to claim 1, it also includes the second n-type semiconductor, wherein second n-type is partly led At least a portion of body separates with the p-type semiconductor ionic charge.

5. heterogeneous material according to claim 4, wherein second n-type semiconductor includes cerium oxide.

6. heterogeneous material according to claim 5, wherein the cerium oxide is CeO₂。

7. heterogeneous material according to claim 4, wherein second n-type semiconductor includes multiphase TiO₂。

8. heterogeneous material according to claim 1, wherein the p-type semiconductor is substantially dispersed in the n-type On semiconductor.

9. heterogeneous material according to claim 1, wherein the form of the p-type semiconductor is with 100nm or smaller Particle diameter particle.

10. heterogeneous material according to claim 1, wherein copper (I)：The ratio of copper (II) is 10:90 to 30:70 it Between.

11. the method for decomposing pollutant, methods described include：In the presence of light, the pollutant is made to be exposed to photochemical catalyst, institute State photochemical catalyst and include heterogeneous material according to claim 1.

12. killing the method for microorganism, methods described includes：In the presence of light, the microbial exposure is made in photochemical catalyst, institute State photochemical catalyst and include heterogeneous material according to claim 1, the microorganism is bacterium or virus.