CN114653385A - Household appliance with a self-cleaning catalytically active surface and method for operating the same - Google Patents

Household appliance with a self-cleaning catalytically active surface and method for operating the same Download PDF

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Publication number
CN114653385A
CN114653385A CN202210304100.8A CN202210304100A CN114653385A CN 114653385 A CN114653385 A CN 114653385A CN 202210304100 A CN202210304100 A CN 202210304100A CN 114653385 A CN114653385 A CN 114653385A
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household appliance
ros
self
water
catalytically active
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M·C·阿塔尔拉奥斯
A·比朔夫
M·A·布努埃尔玛格达莱娜
G·A·拉萨罗比利亚罗亚
J·桑斯纳瓦尔
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BSH Hausgeraete GmbH
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Priority claimed from EP16382519.3A external-priority patent/EP3320972A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • B01J2523/44—Lead
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/47—Titanium
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/62—Sulfur
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/63—Selenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/847—Nickel

Abstract

The invention relates to a household appliance (1) having at least one self-cleaning catalytically active surface (17) containing at least one Reactive Oxygen Species (ROS) generator, wherein the at least one ROS generator is selected from the group consisting of compounds represented by formula (I), (II) or (III); Ag-B-M-S (I), wherein B is selected from the group consisting of Al, Ga, In, Sn, Tl, Pb and Bi, and M is selected from the group consisting of Ti, Zr, Cr, Mo, Mn, Fe, Ru, Ni, Pd, Cu, Zn and Cd; MO (metal oxide semiconductor)q-a (ii), wherein q ═ 2 or 3, M is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn; a is an acetylacetonate or a derivative thereof selected from the group consisting of compounds represented by the formula (A), wherein R1、R2And R3Independently selected from the group consisting of H, Cl, Br, I and C1‑C80Hydrocarbons and polymer radicals. YSe-Rx‑MO2(III) wherein Y is selected from Sn or Pb; rxIs a carbon allotrope; m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn.
Figure DDA0003564145530000011

Description

Household appliance with a self-cleaning catalytically active surface and method for operating the same
The application is a divisional application of an invention patent application with the application date of 2017, 10 and 24, application number of 201780068694.4(PCT/EP2017/077073) and the title of 'household appliance with self-cleaning catalytic active surface and operation method thereof'.
Technical Field
The invention relates to a household appliance having at least one self-cleaning catalytically active surface containing at least one Reactive Oxygen Species (ROS) generator and to a method for operating the same.
Background
Household appliances may come into contact with dust, dirt, food, moisture, or human skin. In the long run, this may lead to hygiene problems, as microorganisms may deposit on the domestic appliance and may proliferate.
Furthermore, food stains are common in household appliances, where they can create a number of problems. Generally, the presence of stains on external components is associated with a poor hygienic feel. Some surfaces are difficult to keep clean, such as stainless steel and glass. Some stains, such as burnt stains, require vigorous cleaning by the user. Food stains can be seen in cooking scenes (hobs, ovens) but also in storage home appliances such as refrigerators.
Furthermore, articles soiled in various ways are generally cleaned in water-bearing domestic appliances. Thus, food residues may occur in a dishwasher and the extent of soil occurring in the laundry to be washed in a washing machine is generally greater. All water-bearing domestic appliances have in common that dirt is generated and accumulates in humid and warm atmospheres, in particular in places which are difficult to access. This fouling may be a good nutrient medium for microorganisms such as bacteria and fungi.
Particularly at locations where water is retained in the household appliance, there are sanitary problems. Therefore, in laundry treatment devices, such as washing machines, when using a water reservoir or often a washing program with cold liquid, during a door closing or a long non-use phase under adverse standing conditions, dirt may be generated, in particular biofilm formation including organic substances such as microorganisms and nutrients. The biofilm causes an unpleasant odor and/or visible fouling. Pathological effects may even occur. Biofilms are particularly formed in areas of the washing machine where water is present for long periods of time, i.e. during non-use phases. These areas include areas of poor ventilation such as ribs, pockets, seal folds, water inlets and outlets, and in particular water reservoirs for storing grey water produced during washing and rinsing for reuse in subsequent washing or rinsing processes. Therefore, it is desirable to disinfect water in home appliances and prevent the formation of biofilm.
Other household appliances that may be easily contaminated by microorganisms are, for example, kitchen hoods or vacuum cleaners.
Regardless of the type of the household appliance, a problem arises that, in order to control the household appliance, the operating panel generally has to be touched by the user. Thus, the operation panel may be contaminated by microorganisms, and when the home appliance is used by a plurality of persons, the microorganisms may be diffused.
In order to maintain a sanitary and non-critical state in household appliances, various methods are currently used. In particular, various measures for removing and/or preventing biofilms are known from the prior art. In water-carrying household appliances, machine cleaning programs are sometimes provided which remove accumulated dirt at high temperatures by means of detergents, sometimes also increasing the liquid level and/or increasing the drum rotation speed, i.e. increasing the input of mechanical energy. It is also known to use ozone to remove organic foulants.
In a well-known method, the use of antimicrobial active ingredients, such as silver ions, in surfaces is envisaged. However, a disadvantage of these antimicrobial active ingredients is that they are gradually removed from the surface and thereby exhausted. In addition, when Ag+Or Cu+Ions also have an adverse effect on groundwater and waterway contamination when used in water-carrying household appliances, for example, in washing liquids and on surfaces of materials in contact with washing liquids. However, if these active ingredients are not washed out of the carrier material in the surface of the household appliance, their efficacy is mostly so small that in the long term, microorganisms and even biofilms can form on the surface of the household appliance and have a negative effect on the state of hygiene of the household appliance.
It has also previously been proposed to remove organic fouling by means of UV-C radiators using the flow-through principle, in such a way that the microorganisms in such fouling are finally killed by destruction of the genetic material.
Other methods involve increasing the temperature at the surface of the member in contact with the wash liquid via direct or indirect energy transfer (water, steam, microwaves) to thermally kill any microorganisms present.
Photocatalytic processes are also known, for example, using catalytically effective compounds, in particular titanium dioxide coatings, for deodorization, disinfection and cleaning. In this process, the catalyst needs to be activated frequently by means of UV radiation. These compounds support the oxidative modification or destruction of microorganisms, so that they are in the best case removed in their entirety oxidatively. However, this method generally operates only in a limited manner, in particular if UV light is additionally required for the oxidation.
A disadvantage of these known methods and measures is the high energy consumption and sometimes high equipment and/or operating costs for achieving a significant effect. In some methods, factors that may be hazardous to health, such as ozone or UV radiation, are used, requiring additional safety measures.
The specific surface structure using the lotus effect aims to reduce the adhesion of dirt and to make the surface easy to clean. These surfaces generally have no antimicrobial effect. A big disadvantage of all these methods is that they work very locally. Therefore, there is no broad range of antimicrobial action in the free water of the water storage container.
Another approach involves the formation of Reactive Oxygen Species (ROS) as an oxidizing agent to remove and/or prevent the growth of microorganisms and the formation of biofilms. The ROS generators currently used in household appliances are polyoxometallate compounds. During the regeneration of reduced polyoxometallate salts, it has been found that polyoxometallates are capable of oxidizing certain organic species and generating Reactive Oxygen Species (ROS) as efficient oxidants. However, a major disadvantage associated with the use of polyoxometallates is that ROS, which are the major catalytic in preventing and removing biofilms, are only generated at a rather low rate. The concentration of ROS is higher in the immediate vicinity of the polyoxometalate source, but the concentration gradient decreases rapidly with increasing distance from the polyoxometalate source. In addition, the low ROS formation rate also affects the lifetime of the polyoxometallate as a catalyst, which should be as long as possible.
The use of polyoxometallates as ROS generators in household appliances is known.
Publication EP 1141210B 1 discloses a method for bleaching laundry or household surfaces, wherein a detergent containing a polyoxometalate is brought into contact with a contaminated substrate. Air is used as the primary source of oxygen atoms for bleaching.
Publication DE 102009026712 a1 discloses a household appliance having at least one component with a surface that can be affected by organic soiling, which surface is provided with a photocatalyst, which household appliance has a light source for irradiating the photocatalyst with activated electromagnetic radiation associated with the surface, which surface is formed from a predominantly formed first material in which the photocatalyst is dispersed. Materials having titanium dioxide and modifications thereof are disclosed in great detail as photocatalysts.
Publications EP 2761073B 1 and US 2014/231363 a1 disclose a water-carrying domestic appliance having a container for receiving an object to be cleaned and at least one inner surface containing a catalytically active substance, which surface is arranged within the domestic appliance, wherein the catalytically active substance is a polyoxometalate and which inner surface is in contact with the water to be cleaned during operation of the domestic appliance. Preferably, the polyoxometalate is a tungstate, even more preferably the tungstate is modified by titanium.
Publication WO 2015/0787737 a1 discloses a water-conducting household appliance having a storage tank for storing a quantity of greywater and a treatment device for treating the greywater stored in the storage tank. The water-conducting household appliance is designed for determining the amount of greywater stored in the water storage tank and for operating a processing device, which is influenced by the determined amount of greywater stored in the water storage tank.
The publications DE 102013205302 a1 and WO 2014/154432 a1 disclose a household appliance which contains at least one catalytically effective substance in the surface, wherein the catalytically effective substance is a polyoxometalate contained in the inner and/or outer surface of the household appliance, with the proviso that if the household appliance is a water-carrying household appliance with a receptacle for receiving an object to be cleaned, the polyoxometalate is contained at least in the outer surface of the household appliance.
Publication WO 2014/122225A 1 discloses the use of heteropolyoxometalates of the formula (I), (II) or (III)
Aq+3PVqZl2-qO40 (I)，
A6P2Z18O62(II), or
A3PZ4O24 (III)
Wherein Z is selected from Mo or W,
the index q is 0, 1, 2 or 3, and
a is selected from one or more cations and comprises at least one cation selected from the group consisting of quaternary ammonium cations, quaternary phosphonium cations and tertiary sulfonium cations for providing self-cleaning, stripping, disinfecting, self-disinfecting, biocidal, antimicrobial and/or deodorizing properties to at least a portion of a substrate or substrate surface or to a coating or for decomposition and/or degradation of organic materials. In formula (I), Z is preferably Mo and q is 2, and in formula (III), Z is preferably W.
Publication EP 2765136A 1 discloses heteropolyoxometalates of the formula (I), (II) or (III)
Aq+3PVqZ12-qO40 (I)，
A6P2Z18O62(II), or
A3PZ4O24 (III)
Wherein Z is selected from Mo or W,
q is 1, 2 or 3, and
a is selected from one or more than two cations and comprises at least one quaternary ammonium cation, with the proviso that compounds [ (n-C)4H9)4N]3PMo12O40And [ (n-C)6H9)4N]3PMo12O40. Most preferred are heteropolyoxometalates [ (n-C)4H9)4N]3PW4O24And [ (n-C)6H13)4N]3PW4O24。
JP 2015066059 a discloses a washing machine which solves the problem of stably eluting silver ions as a sterilizing component without being affected by the concentration of calcium ions contained in water used. Therefore, the washing machine includes a bactericide containing magnesium oxide, zinc oxide and silver oxide at the bottom portion of the rotary tub, which is a portion in contact with water.
KR 20040093958A discloses a water supply chamber for a washing machine using filter balls coated with nano silver. A water supply chamber for a washing machine using nano silver is provided, which supplies water from the outside to the washing machine through a plurality of filter balls by antibacterial action of the filter balls, thereby destroying microorganisms in the water.
CN 204445765U discloses a dishwasher, which comprises a washing chamber disposed at the upper part of a housing and a water tank disposed at the lower part of the housing, wherein a tableware basket and a rotary spray arm are disposed in the washing chamber, the rotary spray arm is communicated with the water tank, a filtering mechanism is installed in a water outlet at the bottom of the washing chamber, a funnel-shaped diversion chute is provided at the bottom of the washing chamber, and a layer of nano silver is coated on the upper surface of the diversion chute.
CN 105837939A describes a composite antibacterial plastic for a refrigerator and a preparation method of the composite antibacterial plastic. The method comprises mixing polypropylene resin and Ag-ZnTiO3Mixing the nano antibacterial agent, the naphthalenedisulfonic acid and magnesium polymer antibacterial agent, the N-acetyl octylamine-4-vinyl pyridine polymer antibacterial agent, the plasticizer, the coupling agent, the stabilizer and the dispersing agent in a high-speed kneader at the rotating speed of 1800-195 revolutions per minute, and extruding the materials in a double-screw extruder at the segmented temperature of 120-195 ℃ to obtain the composite antibacterial plastic for the refrigerator. Mixing inorganic Ag-ZnTiO3The nano antibacterial agent, the naphthalene disulfonic acid magnesium and the N-acetyl octylamine-4-vinyl pyridine organic polymer antibacterial agent are compounded into a synergistic agent. The composite antibacterial plastic has the advantages of stable performance and high antibacterial activity. The nano-scale antibacterial agent is highly dispersed in the resin matrix, and endows the plastic with excellent antibacterial performance.
JP 2001220305 a discloses an antibacterial, mildewproof and algaecidal article comprising a surface portion of the article with distributed antibacterial, mildewproof and algaecidal components and a central portion of the article formed in a deeper portion than the surface portion and substantially free from diffusion of such components; the method for producing an article comprises diffusing the composition from the surface of the article to the inside of the surface portion.
Disclosure of Invention
In view of this situation it is a primary object of the present invention to provide a household appliance and a method of operating the same, providing an improvement in the removal or avoidance or at least a large degree of removal or avoidance of hygiene affecting contaminants.
According to the invention, this object is achieved by a household appliance and a method for operating the same, which are characterized by the features of the respective independent claims. Preferred embodiments of the household appliance according to the invention are disclosed in the respective dependent claims. Preferred embodiments of the household appliance according to the invention correspond to preferred embodiments of the method according to the invention and vice versa, even if not explicitly stated herein.
Accordingly, the present invention relates to a household appliance having at least one self-cleaning catalytically active surface containing at least one Reactive Oxygen Species (ROS) generator, wherein the at least one ROS generator is selected from a compound represented by formula (I), (II) or (III);
Ag-B-M-Sulfur (I)
Wherein the content of the first and second substances,
b is selected from the group consisting of Al, Ga, In, Sn, Tl, Pb, and Bi, M is selected from the group consisting of Ti, Zr, Cr, Mo, Mn, Fe, Ru, Ni, Pd, Cu, Zn, and Cd;
MOq-A (II)
wherein the content of the first and second substances,
q is 2 or 3; and
m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn; and
a is an acetylacetonate or a derivative thereof selected from the group consisting of compounds represented by the following formula:
Figure BDA0003564145510000061
wherein the content of the first and second substances,
R1、R2and R3Independently selected from the group consisting of H, Cl, Br, I and C1-C80Hydrocarbon and polymer radicals;
YSe-Rx-MO2 (III)
wherein the content of the first and second substances,
y is selected from Sn or Pb; and
Rxis a carbon allotrope; and
m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn.
The compounds represented by formula (I), (II) or (III) show a synergistic catalytic effect when compared to the corresponding starting compounds.
The catalytic effect can be measured according to the so-called "switching frequency" (TOF) calculated using the following formula:
Figure BDA0003564145510000071
for example, rhodamine B can be used as a model dye. Rhodamine B has in fact been used in the literature several times to evaluate the performance and subsequent oxidizing capacity of catalysts for the generation of reactive oxygen species (ROS generation) (see, for example, Kalyanamaman B, Darley-Usmar V, Davies KJA et al, "Measuring reactive oxygen and nitrogen species with fluorescent probes: challenges and limitations)," free radical biology and medicine, 2012; 52(1):1-6.doi:10.1016/j. freestrom. 2011.09.030.). There is a direct correlation between ROS generation and antimicrobial activity. To obtain the experimental results discussed herein, rhodamine B was used as the dye.
Preferably, the device is provided, wherein the at least one ROS generator is
Ag-In-Ni-S (I').
In a preferred embodiment, Ag-In-Ni-sulfur is used In the form of a nanocomposite. The nanocomposite can generally be prepared in any suitable manner, such as a hydrothermal process.
In a preferred embodiment, the above compound is prepared by dissolving silver acetate, indium acetate, nickel tetrahydrate, and sodium dodecyl sulfate in water to prepare solution a. Separately, thioacetamide was dissolved in water to prepare solution B. The two solutions a and B are transferred to an autoclave, for example a 25mL teflon lined sealed stainless steel autoclave, and heated, for example by placing the solutions a and B in a pre-heated oven at 130 ℃ for 2 hours, then cooled to room temperature. Then, a black solid precipitate is obtained, typically by centrifugation, followed by washing with deionized water and ethanol, and finally drying under vacuum for 2 hours.
In one specific example, the above compound was prepared, where silver acetate (1.0mmol), indium acetate (1.0mmol), nickel acetate tetrahydrate (1.0mmol), and sodium dodecyl sulfate (0.1-1.15mmol) were dissolved in 10mL of water (solution A). In a separate flask, thioacetamide (3.5mmol) was dissolved in 5mL of water (solution B).
The compounds of formula (I) show a synergistic catalytic effect when compared to the corresponding starting compounds.
For example, measurements under comparable experimental conditions, i.e., using coordinated concentrations of catalyst and dye and experimental time, indicate TOF values [ in min ] of AgSInSNiS in the dark-1Meter]Is 2.14 multiplied by 10-6Whereas for AgS, the TOF value is 7.57X 10-8For NiS, the TOF value is 8.28X 10-9For In2S3TOF value of 7.18X 10-9All of these are measured in the dark. TOF value of AgSInSNiS [ in min ] in sunlight-1Meter for measuring]Is 1.32X 105. These results demonstrate that the catalytic activity and thus the antimicrobial activity of the compounds of formula (I) is increased, whereas the metal sulphide alone was found to be a poor catalyst in the absence of light. Thus, ROS generation is due to the synergistic effect of the nanocomposite and not to the individual components.
It is believed that the electron storage properties of Ag help to turn the apparent fermi level of the composite to a more negative potential and make it a more reducing photocatalyst. This reducing nature of the photocatalyst can provide electrons even under dark conditions. The electrons dissipate at the surface, generating ROS. The generation of photo-induced electron-hole pairs is faster in the presence of different multinary semiconducting chalcogenides, one or both of whichThe above may act as a cocatalyst in the process. In the presence of S2-/Sn2-Hole scavenging in the case of redox couples is effective in scavenging holes from the nanocomposites of formula (I) to maintain their stability throughout the experiment.
Thus, the mechanism proposed herein is based on the electron storage behavior of silver, which promotes the formation of electron-hole pairs even in the absence of light. The generation of electron-hole pairs is faster under visible light. The surface transfer process of the electron-hole pairs on top of the coupled semiconductor nanocomposite makes the semiconductor nanocomposite more suitable for generating ROS. These generated ROS are responsible for antimicrobial properties.
Preferably another household appliance, wherein the at least one ROS generator is
ZrO2-A (II)
Wherein A is acetylacetonate.
In a preferred embodiment, the above-mentioned ZrO2The compound of formula (I) is prepared by a sol-gel process. In this way, after drying the gel at room temperature, the compound can be obtained as a porous amorphous material.
Preferably, the above compound can be obtained by preparing a first solution containing zirconium (IV) acrylate, acetylacetone, and 1-propanol, and adding a second solution containing water and 1-propanol thereto. Stirring is then usually carried out, preferably at a temperature of 20 to 30 ℃ until gelation, and the resulting gel is then dried to give an amorphous product.
In a preferred example, the above compound can be obtained by preparing at room temperature and stirring at room temperature a first solution containing zirconium (IV) propyloxide (70 wt% in 1-propanol, 10mL, 22.6mmol), acetylacetone (99 +%, 1.5mL, 14.6mmol) and 1-propanol (99.80 +%, 3.0mL, 39.9 mmol). A second solution containing distilled water (3.0mL, 166mmol) and 1-propanol (5.5mL, 73.2mmol) was added to the first solution. The resulting solution was then stirred vigorously at room temperature for about 20 minutes until gelation occurred. A homogeneous, pale yellow gel was obtained. The gel was left at room temperature for 24 hours and then dried at 30 ℃ to give a porous amorphous material.
The compounds of formula (II), in particular formula (II'), show a synergistic catalytic effect. The catalytic effect can be measured in terms of the so-called "conversion frequency" (TOF) using the formula described above. The results of the measurements under comparable experimental conditions, i.e. with coordinated concentrations of catalyst and dye and experimental time, show that ZrO2TOF value [ in min ] of ACAC (ACAC: Acetylpyruvate) in the dark-1Meter]Is 2.79X 10-6In contrast, ZrO2TOF value in dark was 2.46X 10-9。
Furthermore, a household appliance is preferred in which the at least one ROS generator is
PbSe-Cx-TiO2(III')
Wherein C isxIs graphene.
The above compounds may be prepared in any suitable manner. In a preferred embodiment, the above compound is obtained by mixing graphene oxide and PbCl2To obtain solution a. Also by mixing Na2SO3And selenium powder dissolved in water and forming Na under reflux2SeSO3To prepare solution B. Then, the solution B and aqueous ammonia were added to the solution A, followed by heating to a temperature of 50 to 80 ℃. Then adding colloidal aqueous TiO2The solution (solution C) was added to the mixture and the suspension was finally sonicated at room temperature. Thereafter, the reaction mixture was cooled to room temperature, washed with water and dried to obtain the desired compound.
In a preferred example, the above compound is obtained by sonicating 300mg of graphene oxide and 1.76g of PbCl for 1 hour2Dispersed in 80mL of ethylene glycol to obtain uniform Graphene Oxide Nanoplatelets (GONS)/Pb2+(solution A). In addition, Na is added2SO3(5g) And selenium powder was dissolved in 30mL of distilled water and refluxed for 1 hour to form Na2SeSO3(solution B). Solution B and 6mL NH4OH (28 wt.%) was added to solution a, which was then heated to 60 ℃ for several minutes. Will have ethanol: H2Colloid T with molar ratio of O to TNB being 35: 15: 4iO2The solution (solution C) was added to the mixture and finally the suspension was sonicated for 0, 1, 3, 5h at room temperature using a controlled serial sonication apparatus. The reaction mixture was cooled to room temperature, and the precipitate was filtered, washed with distilled water, and dried in a vacuum oven at 80 ℃ for 12 hours, and then heat-treated at 500 ℃ for 1 hour.
The compounds of formula (III), in particular formula (II'), show a synergistic catalytic effect. The catalytic effect can be measured in terms of the so-called "conversion frequency" (TOF) using the formula described above. Measurements under comparable experimental conditions, i.e. with coordinated concentrations of catalyst and dye and experimental time, show that,
PbSe-TiO2@ TOF value of graphene in dark [ in min-1Meter]Is 1, 86X 10-6In contrast to PbSe-TiO2TOF value in dark of 7, 00X 10-7，TiO2TOF value under UV light of 3.90X 10-7。
A self-cleaning catalytically active surface may generally be obtained during the manufacture of the inventive household appliance.
In a preferred embodiment, the self-cleaning catalytically active surface is obtainable by mixing at least one ROS generator with the surface forming material before or during its preparation.
In a preferred embodiment of the household appliance, the self-cleaning catalytically active surface is provided on a polymeric body. The at least one ROS generator may be mixed with the polymer material there, to obtain a dispersion or compound of ROS generator and polymer. The dispersion or compound may be subjected to injection molding or extrusion, for example, to form a polymeric body. The polymeric material may be a thermoplastic elastomer, a rigid plastic or an elastomer. In particular, polyacrylates, acrylonitrile-butadiene-rubbers, polytetrafluoroethylenes, silicones, acrylate resins, polyurethane resins, silicone resins, polyester resins, alkyd resins, epoxy resins, phenolic resins and urea-or amine-based resins or mixtures thereof are preferred.
Alternatively, the at least one ROS generator may also be mixed with the monomer prior to polymerization. After polymerization, the resulting ROS generator modified polymer may then be subjected to, for example, compounding processes, pressureless processing techniques such as casting or foaming or compression molding, rolling and calendering, extrusion molding, blow molding or injection molding processes or stretching, thermoforming or printing to form a polymeric body.
In another preferred embodiment of the invention, the self-cleaning catalytically active surface is obtainable by generating a layer containing at least one ROS generator on an article providing the surface.
Such a layer may be formed in various ways, for example via coating or applying a paint or varnish containing at least one ROS generator. Multiple layers may also be formed.
However, in a preferred embodiment, the at least one ROS generator is applied together with a polymeric organic or inorganic binder. The adhesive may preferably be selected from acrylate-based adhesives, polyurethane-based adhesives and silicone-based adhesives.
Suitable acrylate-based adhesives are, for example, Grasoln 2K-Acryllack from Grasoln, WorieeCryl A1220 from Worlee Chemie, Covestro
Figure BDA0003564145510000111
A145, water-reducible polyacrylic acid dispersions of hydroxyl functional groups and polyacrylic acid dispersions from the Covestro company
Figure BDA0003564145510000112
A265BA。
A suitable Polyurethane (PUR) based adhesive is for example ATCOAT Atrepur 340 from ATCOAT company.
Suitable silicone resin-based adhesives are, for example, those from Evonik corporation
Figure BDA0003564145510000113
EF. 2577Low Voc from Dow Corning or Bluesil RES 991 from Bluesil.
In this way, in the production of a domestic appliance, the component to be provided with a self-cleaning catalytically active surface containing at least one ROS generator may then be obtained, for example, by dip-coating the component into a liquid containing a binder and at least one ROS generator.
Furthermore, it is also possible to produce a membrane, wherein the at least one ROS generator is combined with a suitable carrier material and adhesive, such that only a relatively small amount of the at least one ROS generator may be required to cover a large surface area. Such a membrane can be applied to the relevant components in the household appliance, for example by gluing or melt-bonding. Furthermore, such a membrane can be arranged directly in an injection mold and thus be used directly for producing a component of a household appliance.
The self-cleaning catalytically active surface may also be generated by arranging the particles of the at least one ROS generator at the surface of the porous material using a suitable binder. The production thereof is generally related to the position of the surface and the manner of use of the household appliance.
In another preferred embodiment, the self-cleaning catalytically active surface may further comprise a mixture of different ROS generators selected from the group of compounds represented by formula (I), (II) or (III).
Thus, for example, one or more ROS generator compounds may be mixed with the surface-forming material before or during its manufacture and/or one or more ROS generator compounds may be applied in a layer located on said manufacturing surface. In this way, synergistic effects between different ROS generator compounds can be exploited.
Generally, dissolution of the at least one ROS generator from the surface into the surrounding liquid medium or any other consumption should be avoided. In a preferred embodiment, for the ROS generator according to formula (II), a is a derivative of an acetylacetonate selected from the group consisting of compounds having the following formula:
Figure BDA0003564145510000121
wherein R is1、R2And R3Independently selected from the group consisting of H, Cl, Br, I and C1-C80Hydrocarbons and polymer radicals. Even more preferably, R1And R3Independently selected from C20-C80Hydrocarbon and polymer radical, and R2Selected from the group consisting of C1-C10Hydrocarbon radicals. It has been found that in particular the longer chain hydrocarbons contribute to a better embedding of the ROS generator compound into the matrix of the surface.
The home appliance is not limited. However, the household appliance according to a preferred embodiment of the present invention is a water-carrying household appliance. Generally, a water-carrying household appliance is a household appliance that uses water during its operation. The items to be cleaned may in particular be cutlery or clothing items. According to the invention, cleaning is also understood to mean rejuvenation. Thus, the water-bearing household appliance may also be a dryer.
In the case of a water-bearing domestic appliance, it is preferred that the surface is an interior surface which is provided in the interior space of the domestic appliance, said interior surface being in contact with flowing or static water during operation of the domestic appliance. Contact is generally necessary because organic substances in the water of the household appliance are oxidized and thus decomposed by contact with the surface containing the at least one ROS generator.
In the case of a water-bearing domestic appliance, it is preferred that at least one interior surface is provided in the water supply system. Additionally or alternatively, it is preferred that the at least one internal surface is provided in the water reservoir. Then, advantageously, the water reservoir comprises a circulation element and/or an air intake element.
In a preferred embodiment, the water-bearing domestic appliance is a dishwasher or a laundry treatment apparatus or a coffee machine.
In another preferred embodiment, the water-carrying household appliance is a laundry treatment apparatus belonging to the group consisting of a washing machine and a washer-dryer.
The inventive household appliance enables water, for example in a water-carrying household appliance, to be treated in an efficient, economical and environmentally friendly manner, such that organic substances, such as microorganisms and nutrients, are decomposed and biofilm formation in the household appliance can be avoided. In the present invention, the properties of the at least one ROS generator, in particular the specific ROS generator described herein, as an oxidation catalyst or as an oxidizing agent, which does not require activation by radiation and which can also operate without light, are utilized.
In oxidation reactions, ROS generators are typically used as oxidation catalysts in combination with an oxidant. According to the present invention, the oxidizing agent is not limited. Preferably, an oxygen-containing oxidizing agent is used. Oxygen, inorganic or organic peroxides and/or ozone are particularly preferred as oxidizing agents. Among them, oxygen is again particularly preferred as the oxidizing agent, since additional input of potentially harmful or interfering substances can be avoided. Air is preferably used as the oxygen source. However, oxygen may be present in the water, e.g., dissolved in the water. Furthermore, by means of a corresponding movement of the water, a mixing of air and water can take place, for example for forming bubbles in the water, and an air-water mixture of this type can be brought into contact with the surface containing at least one ROS generator, atmospheric oxygen preferably being used as oxidizing agent. Particularly preferably, the air inlet element provides a sufficient amount of oxygen in the water to be treated.
The ROS generators discussed herein may have antimicrobial properties due to their flexible redox behavior. That is, the ROS generator may function as an oxidizing agent and a reducing agent depending on the type of reaction. After reduction of the ROS generator, for example after contact with bacteria or fungi, the reduced form thereof may be regenerated by oxygen. Superoxide ion O is generated in the process2 -As a secondary product. Superoxide ions are also very efficient oxidants. Furthermore, hydroxyl radicals may be formed as additional strong oxidants.
In another embodiment, peroxide or ozone is used as the oxidizing agent.
In household appliances with an ozone generator, ozone may be preferred as the oxidizing agent. Such a household appliance preferably also has an ozone removal device. The surface containing the at least one ROS generator is arranged such that it can be contacted with water and ozone. For example, in a washing machine in which ozone may be introduced into the outer tub, the surface containing the at least one ROS generator is arranged in the outer tub, respectively.
If a peroxide is used as the oxidizing agent, it is preferred to use a peroxide already present in the laundry care product. In this way, the addition of more peroxide can be avoided.
In a preferred household appliance, in particular a water-carrying household appliance, more particularly a washing machine or washer-dryer, according to the invention, the self-cleaning catalytically active surface containing at least one ROS generator is arranged in the detergent dispenser tray or in the outer tub, particularly preferably in the outer tub if peroxide is used as the oxidizing agent. The reason therefore is that peroxides are present in particular in heavy-duty detergents and bleaches, although bleaches are in particular usually added directly to the drum.
Preferably, a user of the laundry treatment apparatus according to one embodiment of the home appliance of the present invention can tell whether heavy detergent or bleach is added or not by means of a selection button. Alternatively, the presence of a strong oxidizing agent such as peroxide or ozone may be determined by means of one or more sensors in the washing machine. In the presence of ozone or peroxide, the operation of the circulation element or the gas inlet element can be dispensed with.
In another preferred household appliance of the invention, the self-cleaning catalytically active surface containing the at least one ROS generator may be provided in a water reservoir of the aerosol generator. In this way, the active oxygen generated in the water reservoir can be distributed throughout the household appliance in the form of an aerosol, preferably carried by the air flow.
As mentioned above, oxygen radicals (or oxygen-containing radical, collectively referred to herein as "oxygen radicals") form at the self-cleaning surface of the domestic appliance containing at least one ROS generator, whether an interior surface or an exterior surface, in the presence of an oxidizing agent such as oxygen, hydrogen peroxide or ozone. When these highly reactive oxygen radicals come into contact with organic substances, including microorganisms, an oxidation reaction occurs, which causes decomposition of the organic substances and/or pathological processes in the microorganisms. Thus, biofilm formation is prevented. For example, organic matter in water in contact with an interior surface of a water-bearing household appliance coated with at least one of the ROS generator compounds described herein is decomposed and thus biofilm formation may be avoided.
In order to enable a continuous oxidation reaction, a sufficient level of mobility of the oxidizing species, e.g. oxygen radicals, generated at the surface containing the at least one ROS generator acting as an oxidation catalyst is preferred. This can be achieved, for example, by recirculating the aqueous medium by means of a pump. In the case where there is generally no flow around the surface containing at least one ROS generator, it may be sufficient to use natural diffusion or convection in the case of temperature differences. Sufficient mobility at the surface can be dispensed with if the desired disinfection is to be achieved first at the surface itself and a wide-range effect of the surrounding medium by means of ROS, for example complete disinfection, can be dispensed with. This is particularly the case for control panels that should be in a hygienic state.
Furthermore, the concentration of the oxidizing agent in the water to be treated should be high enough to achieve a sufficient hygienic effect.
In the household appliance of the invention, it is preferred that the self-cleaning catalytically active surface has an upper layer containing at least one ROS generator, said upper layer having a thickness of 0.01 to 1.5mm, preferably a thickness of 0.01 to 0.5mm, more preferably a thickness of 0.02 to 1mm, even more preferably a thickness of 0.05 to 0.5 mm.
When the at least one ROS generator is used with an acrylate-based adhesive, a polyurethane-based adhesive or a silicone resin-based adhesive, the coating thickness is preferably in the range of 10nm to 500 μm, more preferably in the range of 20nm to 200 μm.
Furthermore, it is preferred that in the domestic appliance the upper layer of the surface has a content of at least one ROS generator in the range of 0.1 to 90 wt. -%, more preferably in the range of 0.5 to 50 wt. -%, even more preferably in the range of 1 to 10 wt. -%, based on the weight of the upper layer (in the following also referred to as "surface layer").
In the household appliance according to the invention, in principle any surface may contain at least one ROS generator. These surfaces may be internal or external surfaces.
The surface containing the at least one ROS generator may be the outer surface of a handle, knob, handle lever, control or a switch such as a light switch, armrest, slider, control dial, slider control or a touch-sensitive (active sensing) surface.
In the laundry dryer as a household appliance according to the invention, the surfaces can be, for example, a container receiving the goods to be dried and a condensate container. In general, all water-carrying parts in a domestic appliance, such as pumps, pipes, valves including their housing, may comprise a surface containing at least one ROS generator.
The inner surface containing the at least one ROS generator may be an inner wall of a water container and/or an inner wall of a flow-through part of a water-carrying household appliance.
The water container may be a water container such as a coffee percolator. Furthermore, all other parts of the percolator which come into contact with water or milk or the like may have a self-cleaning surface which contains at least one ROS generator.
Furthermore, the household appliance according to the present invention further comprises a container in which waste, garbage or used spoiled food is temporarily stored.
Other uses of the invention are for disinfecting surfaces in scales or balances to avoid transfer of pathogenic microorganisms. The scale or balance is therefore also a domestic appliance according to the invention.
In case the household appliance is a washing machine, it is particularly advantageous if the outer tub has a surface containing at least one ROS generator. Biofilm formation is avoided and leaching can be initiated during the washing procedure. Another component in the washing machine is a detergent dispenser tray, wherein biofilm formation can also be avoided.
In a dishwasher as a domestic appliance of the invention, the surface containing at least one ROS generator may assist in activating the bleaching agent, decomposing organic materials and disinfecting tap water and stored water.
Another preferred household appliance according to an embodiment of the present invention is a household appliance for storing, preparing or processing food, and the self-cleaning catalytically active surface is an interior surface arranged in an interior space of the household appliance which is in contact with food and/or food residues during operation of the household appliance.
Thus, the interior surface may be, for example, an inner wall of a toaster, an inner wall of a microwave oven and/or an inner wall and/or a shelf in a refrigerator.
In another preferred embodiment, the interior surface is provided in a container for storing, preparing or processing food. Such a container may be a container such as a food processor or blender or a drawer in a refrigerator or freezer.
In a preferred embodiment, the domestic appliance is a refrigerator, freezer, refrigerator freezer, oven, stove, microwave oven, coffee maker or tea maker or food processor.
In general, the at least one self-cleaning catalytically active surface may also be an external surface of one of the above-mentioned domestic appliances, such as for example a surface of a stove plate or an oven door.
The household appliance according to the invention can also be a vacuum cleaner or a device for cleaning or maintaining floors, wherein the surface containing the at least one ROS generator is in particular in the area of the filter and the nonwoven and the anther sac as well as the means for holding the anthers.
Further examples of household appliances according to the present invention are flow-type heaters; a steam station and a steam iron; air humidifiers and air conditioning units. In these cases, disinfection of the surface and the water to be heated is important. In general, it is also important that, by means of the disinfection of the surface, the transmission of potentially harmful microorganisms or fungi can be avoided in the event of skin contact.
In the case of a kitchen hood as another example of a household appliance according to the invention, a disinfection of the surfaces, in particular of the mesh and the filter mat, and a disinfection treatment of the air is important.
Another important use is on the surface of filter units. The self-cleaning surface as described herein may be a surface in the pile of a dust filter.
Furthermore, the present invention relates to a method for operating a household appliance having at least one self-cleaning catalytically active surface containing at least one Reactive Oxygen Species (ROS) generator, wherein the self-cleaning catalytically active surface is contactable with flowing or static water and/or food residues during operation of the household appliance, wherein the at least one ROS generator is selected from compounds represented by formula (I), (II) or (III);
Ag-B-M-Sulfur (I)
Wherein the content of the first and second substances,
b is selected from the group consisting of Al, Ga, In, Sn, Tl, Pb and Bi, and
m is selected from the group consisting of Ti, Zr, Cr, Mo, Mn, Fe, Ru, Ni, Pd, Cu, Zn and Cd;
MOq-A (II)
wherein the content of the first and second substances,
q is 2 or 3; and
m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn; and
a is an acetylacetonate or a derivative thereof selected from the group consisting of compounds represented by the following formula:
Figure BDA0003564145510000171
wherein the content of the first and second substances,
R1、R2and R3Independently selected from the group consisting of H, Cl, Br, I and C1-C80Hydrocarbon and polymer radicals;
YSe-Rx-MO2 (III)
wherein the content of the first and second substances,
y is selected from Sn or Pb; and
Rxis a carbon allotrope; and
m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn.
The advantage of the invention is that an easy-to-clean household appliance, in particular a water-conducting household appliance, is provided in a simple and cost-effective manner, which has a significantly lower sensitivity to dirt, in particular to dirt involving microorganisms.
One particular advantage of using the ROS generator described herein in a surface, particularly an interior surface, is that the lifetime of the ROS generator compounds described herein exceeds the lifetime of known polyoxometallates. The surface can be operated for a longer time without any additional activation or additional energy consumption. The use of only an additional circulation element or an air intake element requires additional energy, but still requires only a small amount of additional energy compared to other water treatment methods such as membrane filtration or electrochemical treatment.
Furthermore, the effectiveness of the catalytically active surface of the present invention exceeds that of polyoxometalate containing surfaces because the rate of active oxygen generation is higher, sometimes significantly higher. In this way, a relatively high concentration of active oxygen may also be maintained at a relatively large distance from the self-cleaning catalytically active surface. Also, for the ROS generator according to the invention, no additional reagents need to be added, and activation of the catalyst, e.g. by UV radiation, may be dispensed with.
Drawings
In the following, the invention will be described in more detail with reference to fig. 1.
Fig. 1 is a schematic view of the currently relevant components of one embodiment of a household appliance according to the invention, configured as a laundry washing machine, as a non-limiting example.
Detailed Description
The washing machine 1 of the present embodiment has a tub 2, and a drum 3 is rotatably mounted in the tub 2 and can be driven by a driving motor 15. For ergonomic reasons, the axis of rotation 4 of the drum 3 is oriented at a small angle upwards away from the horizontal, so that the inner space of the drum 3 is easier to access and inspect. By this arrangement, in cooperation with the specially formed laundry agitator 5 and the scooping means 6 for the washing liquid 7 at the inner surface of the drum jacket, an intensification of the flow of the washing liquid 7 through the laundry 8 can be achieved.
The washing machine 1 also has a water supply system comprising a water connection fixture for a domestic water supply 9, an electrically controlled valve 10 and a supply pipe 11 extending to the outer tub 2 and supplied via a detergent dispenser tray 12 from which a supply liquid can transport the detergent portion to the outer tub 2.
A heating device 14 is also provided in the outer tub 2. The valve 10 and the heating device 14 may be controlled by the program control system 13 according to a program execution plan, which may be linked to a time program and/or to obtaining specific measurements of parameters within the laundry washing machine 1, such as the liquid level, the liquid temperature, the rotation speed of the drum 3, etc. 16 denotes a pump for liquid in the outer tub 2, in particular washing liquid 7.
The water reservoir 18 may store grey water that has been used to rinse the laundry 8. The grey water may be used for a subsequent wash cycle. To this end, a water reservoir 18 is connected via a conduit ("supply pipe for rinsing liquid") 19 to the valve 10, which also regulates the fresh water supply. A circulation element 20 and an air inlet element 21, which can also be controlled by the program control system 13, are provided in the reservoir 18. By these measures, a particularly efficient oxidation reaction can be carried out at the inner surface 17 of the reservoir 18.
An internal surface 17 containing Ag-In-Ni-sulphur In the form of a nanocomposite is applied In the detergent dispenser tray 12, In the outer tub 2 and In the water reservoir 18.
List of reference numerals
1 household appliance, Water-carrying household appliance, washing machine
2 (outer) barrel
3 clothes drum
4 axis of rotation of the drum
5 clothes stirrer
6 scooping device
7 washing liquid
8 item of clothing
9 domestic water supply
10 valve
11 supply pipe
12 detergent dispenser tray
13 program control system
14 heating device
15 driving motor
16 pump
17 interior surface containing ROS Generator
18 water reservoir
19 supply pipe for rinsing water
20 circulation element
21 air intake element

Claims (13)

1. A household appliance (1) having at least one self-cleaning catalytically active surface (17) containing at least one Reactive Oxygen Species (ROS) generator, characterized in that said at least one ROS generator is a compound represented by the formula:
YSe-Rx-MO2
wherein the content of the first and second substances,
y is selected from Sn or Pb; and
Rxis a carbon allotrope; and
m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn.
2. The household appliance (1) according to claim 1, wherein said at least one ROS generator is:
PbSe-Cx-TiO2 (III')
wherein CxIs graphene.
3. Household appliance (1) according to claim 1 or 2, wherein said self-cleaning catalytically active surface (17) is obtainable by mixing at least one ROS generator with a surface-forming material before or during its manufacture.
4. Household appliance (1) according to any of claims 1-3, wherein said self-cleaning catalytically active surface (17) is obtainable by forming a layer containing at least one ROS generator on an article providing said surface.
5. The household appliance (1) according to claim 4, wherein said self-cleaning catalytically active surface (17) has an upper layer containing at least one ROS generator, said upper layer having a thickness of 0.01 to 0.5 mm.
6. Household appliance (1) according to any of claims 1 to 5, wherein the household appliance (1) is a water-carrying household appliance (1) and the self-cleaning catalytically active surface (17) is an internal surface (17) provided in an interior space of the household appliance (1), which internal surface is in contact with flowing or static water during operation of the household appliance (1).
7. The household appliance (1) according to claim 6, wherein said inner surface (17) is provided in a water reservoir.
8. Household appliance (1) according to any of claims 1 to 7, wherein the household appliance (1) is a dishwasher, a laundry treatment device, a coffee machine or a tea maker.
9. The household appliance (1) according to claim 8, wherein the household appliance (1) is a laundry treatment apparatus belonging to the group consisting of a washing machine (1) and a washer-dryer.
10. Household appliance (1) according to any of claims 1 to 5, wherein the household appliance (1) is a household appliance for storing, preparing or processing food, the self-cleaning catalytically active surface (17) being an internal surface (17) provided in an interior space of the household appliance (1), which internal surface is in contact with food and/or food residues during operation of the household appliance.
11. The household appliance (1) according to claim 10, wherein said inner surface (17) is provided in a container for storing, preparing or processing food.
12. The household appliance (1) according to any one of claims 1 to 5, 10, 11, wherein the household appliance (1) is a refrigerator, a freezer, a refrigerator freezer, an oven, a stove, a microwave oven, a coffee or tea maker, or a food processor.
13. Method for operating a household appliance (1) having at least one self-cleaning catalytically active surface (17) containing at least one Reactive Oxygen Species (ROS) generator, wherein the self-cleaning catalytically active surface (17) is in contact with flowing or static water and/or with food or food residues during operation of the household appliance (1), wherein the at least one ROS generator is a compound represented by the formula:
YSe-Rx-MO2
wherein the content of the first and second substances,
y is selected from Sn or Pb; and
Rxis a carbon allotrope; and
m is selected from the group consisting of Zr, Ti, Cr, Mo, W and Mn.
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