Refrigerator

Abstract

Provided is a refrigerator in which a deodorizing filter can exhibit excellent deodorizing performance for a long period of time. Provided is a refrigerator comprising: an inner case forming a storage chamber; a body including an outer case as an outer layer of the inner case; a door configured to open and close the storage chamber; and a deodorizing device disposed on the inner surface of the storage chamber, wherein the deodorizing device includes a deodorizing filter, the deodorizing filter includes a substrate and a deodorizing film on the surface of the substrate, the deodorizing film contains a deodorizing catalyst, and the deodorizing catalyst includes δ-type MnO2 and CeO2, and has a structure in which CeO2 particles are covered with δ-type MnO2, the CeO2-covering δ-type MnO2 having an average particle size of 20 µm or less, and having a specific surface area of at least 250m2 / g in terms of BET value.

Description

refrigerator

[0001] The present invention relates to a refrigerator including a deodorizing catalyst that adsorbs and decomposes odor molecules, a deodorizing film, and a deodorizing filter.

[0002] For example, a deodorizing catalyst using a mixture of δ-type manganese dioxide (MnO2) and cerium oxide (CeO2) is known as a deodorizing filter used in conventional air purifiers or refrigerators, as described in Patent Document 1.

[0003] [Prior Art Literature]

[0004] [Patent Document]

[0005] Patent Document 1: Japanese Patent Laid-Open Publication No. 2021-130104

[0006] δ-type MnO2 has a layered structure, and thus, compared to α-type MnO2 with small pore diameters forming a tunnel-like structure, it has the property of easily adsorbing odor molecules such as formaldehyde. This δ-type MnO2 exhibits a deodorizing function (catalytic function) that oxidizes and decomposes the adsorbed odor molecules. In addition, CeO2 exhibits the function of a cocatalyst that regenerates the catalytic function of δ-type MnO2 by supplying oxygen to the δ-type MnO2. A cocatalyst is a substance that is added to a main catalyst to improve the activity, selectivity, and stability of the main catalyst. For example, δ-type MnO2 is a main catalyst and CeO2 is a cocatalyst.

[0007] In these deodorizing catalysts, it is required that they be able to exhibit better deodorizing performance for a longer period of time when applied to a deodorizing filter.

[0008] The present invention was made to solve the above problem, and its main task is to provide a refrigerator in which a deodorizing filter used in the refrigerator can exhibit excellent deodorizing performance for a long period of time.

[0009] Home appliances such as refrigerators, air purifiers, and air conditioners according to the present invention are as follows.

[0010] According to one embodiment, a refrigerator is provided, comprising: an inner case forming a storage compartment; a body including an outer surface of an outer layer of the inner case; a door configured to open and close the storage compartment; and a deodorizing device disposed on an inner surface of the storage compartment, wherein the deodorizing device includes a deodorizing filter, the deodorizing filter includes a substrate; and a deodorizing film on a surface of the substrate, the deodorizing film including a deodorizing catalyst, the deodorizing catalyst containing δ-type MnO2 and CeO2, having a structure in which CeO2 is coated with δ-type MnO2, and the average particle diameter of the catalyst having this structure is 20 μm or less.

[0011] In another implementation, the specific surface area is 250 m in BET value. 2 A refrigerator with a capacity of / g or more is provided.

[0012] According to another embodiment, a refrigerator is provided, wherein the content of δ-type MnO2 is 90 wt% or more and 99.5 wt% or less, and the content of CeO2 is 0.5 wt% or more and 10 wt% or less.

[0013] According to another embodiment, a refrigerator is provided, wherein the average particle size of δ-type MnO2 coated with CeO2 is 20 μm or less.

[0014] According to another embodiment, a refrigerator is provided, wherein the δ-type MnO2 has a layered structure, and the distance between adjacent layers included in the layered structure is 7 Å or more.

[0015] According to another embodiment, a refrigerator is provided, wherein the deodorizing film further contains an inorganic binder.

[0016] According to another embodiment, a refrigerator is provided, wherein the deodorizing film further contains activated carbon.

[0017] According to another embodiment, a refrigerator is provided, wherein the deodorizing film further contains at least one selected from MgO, FeO, Fe2O3, ZrO2, CuO, NiO, Mn3O4, Co3O4, Al2O3, Y2O3, ZnO, MoO3, IrO2, WO3, W2O3 and TiO2.

[0018] According to another embodiment, a refrigerator is provided, wherein the substrate has a honeycomb structure.

[0019] According to another embodiment, a refrigerator is provided that further includes an ultraviolet light source for regenerating the deodorizing catalyst.

[0020] According to one embodiment, a body having an inlet and an outlet; a fan for moving air so as to discharge air drawn into the inlet to the outlet; a deodorizing device disposed between the inlet and the outlet, wherein the deodorizing device includes a deodorizing filter, the deodorizing filter includes a substrate; and a deodorizing film on a surface of the substrate, wherein the deodorizing film includes a deodorizing catalyst, wherein the deodorizing catalyst contains δ-type MnO2 and CeO2, and has a structure in which CeO2 is coated with δ-type MnO2, and the average particle diameter of the δ-type MnO2 is 20 μm or less, and the specific surface area is 250 m in terms of BET value. 2 / g or more, an air purifier is provided.

[0021] According to another embodiment, an air purifier is provided, wherein the content of δ-type MnO2 is 90 wt% or more and 99.5 wt% or less, and the content of CeO2 is 0.5 wt% or more and 10 wt% or less.

[0022] According to another embodiment, an air purifier is provided, wherein the average particle size of δ-type MnO2 coated with CeO2 is 20 μm or less.

[0023] According to another embodiment, an air purifier is provided, wherein the deodorizing film further contains an inorganic binder.

[0024] According to another embodiment, an air purifier is provided, wherein the deodorizing film further contains activated carbon.

[0025] According to another embodiment, an air purifier is provided, wherein the deodorizing film further contains at least one selected from MgO, FeO, Fe2O3, ZrO2, CuO, NiO, Mn3O4, Co3O4, Al2O3, Y2O3, ZnO, MoO3, IrO2, WO3, W2O3 and TiO2.

[0026] According to another embodiment, an air purifier is provided, wherein the above-described device has a honeycomb structure.

[0027] According to one embodiment, a body having an inlet and an outlet; a fan for moving air so as to discharge the air drawn into the inlet to the outlet; a heat exchanger for heat-exchanging the air drawn into the inlet and a refrigerant; a deodorizing device disposed between the inlet and the outlet, wherein the deodorizing device includes a deodorizing filter, the deodorizing filter includes a substrate; and a deodorizing film on a surface of the substrate, wherein the deodorizing film includes a deodorizing catalyst, wherein the deodorizing catalyst contains δ-type MnO2 and CeO2, and has a structure in which CeO2 is coated with δ-type MnO2, and the average particle diameter of the δ-type MnO2 is 20 μm or less, and the specific surface area is 250 m in terms of BET value. 2 / g or more, home appliances are provided.

[0028] According to the present invention configured in this manner, a refrigerator is provided in which a deodorizing filter used in the refrigerator can exhibit excellent deodorizing performance for a long period of time.

[0029] According to the present invention configured in this manner, an air purifier is provided that can exhibit excellent deodorizing performance for a long period of time in a deodorizing filter used in the air purifier.

[0030] According to the present invention configured in this manner, a home appliance is provided that can exhibit excellent deodorizing performance for a long period of time in a deodorizing filter used in the home appliance.

[0031] FIG. 1 is a perspective view of a refrigerator according to one embodiment of the present disclosure.

[0032] FIG. 2 is a front view showing the interior of a refrigerator according to one embodiment of the present disclosure.

[0033] FIG. 3 is a cross-sectional view of a refrigerator according to one embodiment of the present disclosure.

[0034] FIG. 4 is a perspective view showing the exterior of an air purifier according to an embodiment of the present disclosure.

[0035] Fig. 5 is a cross-sectional view showing the interior of an air purifier according to another embodiment of the present disclosure.

[0036] FIG. 6 is a perspective view showing the exterior of an air conditioner according to an embodiment of the present disclosure.

[0037] Fig. 7 is a cross-sectional view showing the interior of an air conditioner according to an embodiment of the present invention.

[0038] Fig. 8 is a drawing schematically showing the structure of a deodorizing filter, a deodorizing film, and a deodorizing catalyst of the present embodiment.

[0039] Figure 9 is an SEM image of the deodorizing catalyst of the present embodiment (Example 4 in Experimental Example 1).

[0040] Figure 10 is EDX mapping performed on the deodorizing catalyst of the present embodiment (Example 4 in Experimental Example 1).

[0041] Figure 11 is an SEM image of the surface of the deodorizing catalyst of Comparative Example 4 in Experimental Example 1.

[0042] Figure 12 is EDX mapping performed on the deodorizing catalyst of Comparative Example 4 in Experimental Example 1.

[0043] Figure 13 is a reaction formula that the deodorizing catalyst of the present embodiment shows for an odor component.

[0044] Figure 14 is a drawing explaining a new academic discovery regarding the decomposition of odor molecules by the deodorizing catalyst of the present invention.

[0045] Figure 15 is a drawing showing the test conditions, test results, etc. of Experimental Example 2.

[0046] Figure 16 is a drawing showing the test conditions, test results, etc. of Experimental Example 3.

[0047] Fig. 17 is a diagram showing the principle of promoting regeneration of a catalyst by UV irradiation.

[0048] It should be understood that the various implementations of the present disclosure and the terminology used therein are not intended to limit the technical features described in the present disclosure to specific implementations, but rather to encompass various modifications, equivalents, or alternatives of the implementations.

[0049] In connection with the description of the drawings, similar reference numerals may be used for similar or related components.

[0050] The singular form of a noun corresponding to an item may include one or more of said items, unless the relevant context clearly indicates otherwise.

[0051] In this disclosure, each of the phrases "A or B", "at least one of A and B", "at least one of A or B", "A, B, or C", "at least one of A, B, and C", and "at least one of A, B, or C" may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0052] The term "and / or" includes any combination of a plurality of related described elements or any one of a plurality of related described elements.

[0053] Terms such as "first," "second," or "first" or "second" may be used simply to distinguish one component from another and do not qualify the components in any other respect (e.g., importance or order).

[0054] In addition, terms such as 'front', 'rear', 'top', 'bottom', 'side', 'left', 'right', 'upper', and 'lower' used in the present disclosure are defined based on the drawings, and the shape and position of each component are not limited by these terms.

[0055] Terms such as "include" or "have" are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the present disclosure, but do not preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

[0056] When a component is said to be “connected,” “coupled,” “supported,” or “in contact with” another component, this includes not only cases where the components are directly connected, coupled, supported, or in contact, but also cases where the components are indirectly connected, coupled, supported, or in contact through a third component.

[0057] When we say that a component is "on" another component, this includes not only cases where the component is in contact with the other component, but also cases where there is another component between the two components.

[0058] In this disclosure, the “size” of a particle refers to the “particle diameter” of the particle unless otherwise defined.

[0059] In the present disclosure, the "particle diameter" of a particle refers to the average diameter when the particle is spherical, and refers to the average major axis length when the particle is non-spherical. The particle diameter of a particle can be measured using a particle size analyzer (PSA). The "particle diameter" of a particle is, for example, the "average particle diameter." The "average particle diameter" is, unless explicitly stated otherwise, the median particle diameter (D50). The median particle diameter (D50) is the size of the particle corresponding to the 50% cumulative value calculated from the particle side having the smallest particle size in a cumulative distribution curve of particle sizes in which particles are accumulated in order of particle size from the smallest particle to the largest particle. The cumulative value can be, for example, the cumulative volume. The median particle diameter (D50) can be measured, for example, by laser diffraction. Alternatively, the "average particle diameter" can be measured manually or by software from a scanning electron microscope (SEM) image or a transmission electron microscope (TEM) image.

[0060] In the present disclosure, a “refrigerator” is a home appliance that supplies cold air generated by a compressor of a cold air supply device to a storage room to keep various foods fresh for a long period of time.

[0061] A refrigerator may include, for example, a body, which may include an inner case and an outer case disposed outside the inner case. The refrigerator may include, for example, an insulating material disposed between the inner case and the outer case.

[0062] In the present disclosure, the "inner case" refers to a component forming a storage compartment. The inner case may include, for example, a case, a plate, a panel, or a liner. The inner case may be formed as a single body, or may be formed by assembling a plurality of plates.

[0063] In the present disclosure, the "outer case" refers to a member forming the outer appearance of the main body. The outer case may be joined to the outer side of the inner case so that an insulating material is placed between the inner case and the outer case.

[0064] In the present disclosure, a "storage compartment" refers to a space within a refrigerator for storing items. The storage compartment may include, for example, a space defined by an inner box. The storage compartment may further include, for example, an inner box defining a space corresponding to the storage compartment. The storage compartment may store various items, such as food, medicine, and cosmetics, and may be configured such that at least one side is open for inserting and removing items.

[0065] A refrigerator may, for example, include one or more storage compartments. When a refrigerator has two or more storage compartments, each compartment may have a different purpose and be maintained at different temperatures. To achieve this, each storage compartment may be separated from the others by a partition wall containing insulation.

[0066] Storage rooms may be designed to maintain appropriate temperature ranges, for example, depending on their intended use, and may include "refrigerators," "freezers," and / or "variable temperature rooms," which are distinguished by their intended use and / or temperature range. Refrigerators may be maintained at temperatures appropriate for refrigerated storage, for example. Freezers may be maintained at temperatures appropriate for frozen storage, for example.

[0067] As used herein, "refrigeration" means cooling an item to a temperature that does not freeze. For example, a refrigerator may be maintained at a temperature ranging from 0 degrees Celsius to +7 degrees Celsius.

[0068] As used herein, "freezing" means cooling an item to keep it frozen or in a frozen state. For example, a freezer may be maintained at a temperature ranging from -20 degrees Celsius to -1 degree Celsius.

[0069] The variable temperature room can be used as either a refrigerator or a freezer, with or without the user's choice.

[0070] Storage rooms may be referred to by various names, including "refrigerator," "freezer," and "variable temperature room," as well as "vegetable room," "fresh room," "cooling room," and "ice room." The terms "refrigerator," "freezer," and "variable temperature room" used hereinafter should be understood to encompass storage rooms with corresponding uses and temperature ranges.

[0071] The refrigerator may include at least one door configured to open and close an open side of the storage compartment.

[0072] In the present disclosure, a "door" is a member provided to open and close one or more storage compartments, or a single door provided to open and close multiple storage compartments. The door may be installed on the front of the main body in a rotational or sliding manner.

[0073] The door may be configured to seal the storage compartment when the door is closed, for example. The door may include insulation, similar to the body, to insulate the storage compartment when the door is closed, for example.

[0074] The door may include, for example, a door outer panel forming the front of the door, a door inner panel forming the back of the door and facing the storage compartment, an upper cap, a lower cap, and door insulation provided inside these.

[0075] The door inner panel may be provided with a gasket, for example, that seals the storage compartment by pressing against the front of the body when the door is closed. The door inner panel may include a dyke that protrudes rearward to accommodate a door basket for storing items, for example.

[0076] A door may include, for example, a door body and a front panel detachably connected to the front side of the door body and forming the front of the door. The door body may include, for example, a door outer panel forming the front of the door body, a door inner panel forming the rear of the door body and facing the storage compartment, an upper cap, a lower cap, and door insulation provided inside these.

[0077] Refrigerators can be classified into French door type, side-by-side type, bottom mounted freezer (BMF), top mounted freezer (TMF), or single-door refrigerators, for example, depending on the arrangement of the door and storage compartment.

[0078] The refrigerator may include a cold air supply device arranged to supply cold air to the storage compartment.

[0079] In this disclosure, “refrigeration supply device” means a machine, mechanism, electronic device and / or a system combining these that can generate cold air and guide the cold air to cool a storage room.

[0080] A refrigeration supply device can generate cold air through a refrigeration cycle that includes the processes of compression, condensation, expansion, and evaporation of a refrigerant. To this end, the refrigeration supply device can include a compressor, a condenser, an expansion device, and an evaporator capable of driving the refrigeration cycle.

[0081] The refrigerator may include a mechanical room in which at least some components belonging to the refrigeration supply unit are arranged.

[0082] In this disclosure, the term "machine room" refers to a space where at least some components belonging to a refrigeration supply device are placed. To prevent heat generated by components placed in the machine room from being transferred to the storage room, the machine room may be provided with partitions and insulation. To dissipate heat from components placed within the machine room, the interior of the machine room may be configured to be connected to the exterior of the main body.

[0083] The refrigerator may further include a dispenser provided on the door to provide water and / or ice. The dispenser may be provided on the door so that it is accessible to the user without having to open the door.

[0084] A refrigerator may include an ice-making device configured to produce ice. The ice-making device may include an ice-making tray that stores water, an ice-discharging device that separates ice from the ice-making tray, and an ice bucket that stores ice produced in the ice-making tray.

[0085] In the present disclosure, an “air purifier” is a home appliance that draws in polluted air from an indoor space, removes dust, odor, etc. contained in the air, and then discharges the purified air obtained to the outside.

[0086] An air purifier includes, for example, a main body, which includes an intake port and an exhaust port.

[0087] In this disclosure, an "intake" is an opening that draws contaminated air from an indoor space into the body. An intake is an opening, structure, or system through which fluid flows into the body due to a pressure difference between the outside and inside. The flow rate through the intake depends on factors such as the pressure difference, fluid properties, and the shape of the intake.

[0088] In this disclosure, a "discharge port" is an opening that discharges purified air into an indoor space outside the main body. A discharge port is an opening, structure, or system through which fluid is discharged outside the main body due to a pressure difference between the outside and inside. The flow rate through the discharge port depends on factors such as the pressure difference, fluid characteristics, and the shape of the discharge port.

[0089] The air purifier includes a fan placed inside the body and a fan motor for driving the fan.

[0090] In the present disclosure, a "fan" is a member that moves air so that air drawn into the interior of the body through an intake port is discharged to the exterior of the body through an exhaust port. A fan is a member that causes air to move by rotating fan blades connected to a rotating shaft.

[0091] In the present disclosure, a “fan motor” is a member connected to the rotational shaft of the fan and providing rotational force to rotate the fan blades.

[0092] The air purifier may include a sensor to detect the status of the air purifier.

[0093] In the present disclosure, a "sensor" can detect one or more of the current and voltage input to the fan motor, the wind speed at the outlet side, and the wind speed at the intake side. The sensor can include, for example, a fan motor sensor, a wind speed sensor, etc. The fan motor sensor can be positioned to measure the current and voltage input and output to the fan motor. The wind speed sensor can be positioned around the outlet to detect the wind speed at the outlet side.

[0094] The air purifier may include an input unit, a display unit, and an output unit for operating the air purifier.

[0095] In the present disclosure, the "input unit" is provided on the outside of the main body and can receive various control commands from the user. Each input button of the input unit may be a push switch or membrane switch that generates an input signal through pressure from the user, or a touch switch that generates an input signal through touch of a part of the user's body.

[0096] In the present disclosure, the "display unit" is a configuration for displaying the operating status of the air purifier. The display unit may, for example, quantitatively or qualitatively display indoor air quality.

[0097] In this disclosure, the "output unit" is a configuration for displaying the operating status of the air purifier in the form of sound. The output unit may output air quality information in the form of a guidance voice, a melody, or the like, for example.

[0098] In the present disclosure, an “air conditioner” is a home appliance that draws air from an indoor space, cools the drawn air, and then discharges the cooled air to the outside.

[0099] An air conditioner includes, for example, a body, and the body includes an intake port and an exhaust port.

[0100] In the present disclosure, an “intake port” is an opening through which indoor air is sucked into the interior of the main body.

[0101] In the present disclosure, an “outlet” is an opening that discharges cooled air into an indoor space outside the main body.

[0102] The air conditioner includes a fan and a fan motor placed inside the body.

[0103] In the present disclosure, a "fan" is a member that moves air so that air drawn into the interior of the body through an intake port is discharged to the exterior of the body through an exhaust port. A fan is a member that causes air to move by rotating fan blades connected to a rotating shaft.

[0104] In the present disclosure, a “fan motor” is a member connected to the rotational shaft of the fan and providing rotational force to rotate the fan blades.

[0105] The air conditioner includes a heat exchanger that exchanges heat between the air drawn into the intake and the refrigerant.

[0106] In this disclosure, a "heat exchanger" is a system used to transfer heat between a heat source and a working fluid. Heat exchangers are used in cooling processes. The working fluid, i.e., refrigerant, is separated by a solid wall to prevent mixing with the heat source, i.e., introduced air.

[0107] A refrigerator, air purifier or air conditioner may each include a processor to control them.

[0108] In this disclosure, a "processor" controls the overall operation of a refrigerator, air purifier, or air conditioner. A processor refers to a hardware device (chip) that includes an integrated circuit in which electrical circuits are integrated. The processor can control components of the refrigerator, air purifier, or air conditioner by executing a program stored in memory. The processor may include a separate NPU that performs the operation of an artificial intelligence model. The processor may also include a central processing unit, a graphics processor (GPU), or the like. The processor may generate a control signal for controlling the operation of a cooling device, for example. For example, the processor may receive temperature information of a storage compartment from a temperature sensor and generate a cooling control signal for controlling the operation of the cooling device based on the temperature information of the storage compartment.

[0109] The processor can process user input of a user interface and control the operation of the user interface based on programs and / or data stored / stored in memory. The user interface can be provided using an input interface and an output interface. The processor can receive user input from the user interface. In response to the user input, the processor can transmit display control signals and image data to the user interface for displaying an image on the user interface.

[0110] In the present disclosure, "memory" stores or records various information, data, commands, programs, etc. required for the operation of a refrigerator, air purifier, or air conditioner. Memory refers to a hardware device (chip) that includes an integrated circuit in which electrical circuits are integrated. The memory can store temporary data generated during the generation of control signals for controlling components included in the refrigerator, air purifier, or air conditioner. The memory may include at least one of volatile memory and non-volatile memory, or a combination thereof. The processor and memory may be provided integrally or separately. The processor may include one or more processors. For example, the processor may include a main processor and at least one sub-processor. The memory may include one or more memories.

[0111] A refrigerator, air purifier, or air conditioner may, for example, include a processor and memory that control all of the components included in each of them, and may also include multiple processors and multiple memories that individually control each of these components. For example, a refrigerator may include a processor and memory that control the operation of a cooling device based on the output of a temperature sensor. A refrigerator may also include a separate processor and memory that control the operation of a user interface based on user input.

[0112] In the present disclosure, a “control unit” means a part including a memory that stores or memorizes a program and / or data for controlling a refrigerator, air purifier, or air conditioner, and a processor that outputs a control signal for controlling a cooling air supply device, a fan motor, a heat exchanger, etc. according to the program and / or data stored in the memory.

[0113] The communication module can communicate with external devices such as servers, mobile devices, and other home appliances via a nearby access point (AP). The AP can connect the local area network (LAN) to which the refrigerator, air purifier, air conditioner, or user device is connected to the wide area network (WAN) to which the server is connected. The refrigerator, air purifier, air conditioner, or user device can then connect to the server via the wide area network (WAN).

[0114] The input interface may include keys, a touchscreen, a microphone, etc. The input interface may receive user input and transmit it to the processor.

[0115] The output interface may include a display, a speaker, etc. The output interface may output various notifications, messages, information, etc. generated by the processor.

[0116] Hereinafter, home appliances such as refrigerators, air purifiers, and air conditioners including a deodorizing filter according to one embodiment of the present invention will be described with reference to drawings.

[0117] FIG. 1 is a perspective view of a refrigerator according to an embodiment of the present disclosure. FIG. 2 is a front view showing the interior of a refrigerator according to an embodiment of the present disclosure. FIG. 3 is a cross-sectional view of a refrigerator according to an embodiment of the present disclosure.

[0118] Referring to FIGS. 1 and 2, a refrigerator (1000) according to one embodiment of the present disclosure includes a main body (1) having a storage compartment (2, 2a, 2b) and a door (3, 3a, 3b, 3c, 3d) coupled to the main body (1) to open and close the storage compartment. The main body (1) of the refrigerator (100) includes an inner case; and an outer case disposed on the outside of the inner case. The refrigerator (1000) includes a door (3, 3a, 3b, 3c, 3d) configured to open and close an open side of the storage compartment (2). The refrigerator (1000) is illustrated with four doors (3), but the number of doors (3) is not limited thereto. The upper door (3a) and the lower door (3b) on the right side of the refrigerator (1000) may be configured as one door, and the upper door (3c) and the lower door (3d) on the left side of the refrigerator (1000) may be configured as one door. In addition, the number of doors of the refrigerator (1000) may be more or less than four. In addition, the positions of the doors (3) may also be varied. Between the plurality of doors (3a, 3b, 3c, 3d), a handle area (4) may exist as a space where a user can insert a hand to open and close the door (3). The door (3) may be configured to seal the storage compartment when the door (3) is closed.

[0119] Referring to FIG. 3, a refrigerator (1000) according to one embodiment of the present disclosure includes a main body (1) having a storage compartment (2) and a door (3) coupled to the main body (1) to open and close the storage compartment. The refrigerator (1000) includes refrigeration cycle components such as a compressor (11), a condenser (not shown), an evaporator (12), and an expansion valve (not shown). Cold air generated in the evaporator (12) is supplied to the storage compartment (2) through a blower (13), so that the storage compartment (2) is maintained at a low temperature. The refrigerator (1000) includes a deodorizing device (20) for removing odors generated from food, etc. stored in the storage compartment (2). The deodorizing device (20) is arranged on the inner surface of the storage compartment (2). The deodorizing device (20) may be installed, for example, on the upper rear side of the storage compartment (2). The deodorizing device (20) includes a deodorizing filter (not shown). A deodorizing device (20) includes, for example, a housing (not shown) that forms a passage through which air passes; a deodorizing filter (not shown) that is disposed on the passage inside the housing (not shown) and removes odor; and a fan (not shown) that allows air in a storage chamber (2) to pass through the passage inside the housing (not shown) and the deodorizing filter (not shown) disposed on the passage. The deodorizing device (20) may further include a filter light source (not shown) that irradiates light onto the deodorizing filter to regenerate the deodorizing filter. The filter light source may, for example, irradiate ultraviolet rays to regenerate the deodorizing filter.

[0120] Fig. 4 is a perspective view illustrating the exterior of an air purifier according to one embodiment of the present disclosure. Fig. 5 is a cross-sectional view illustrating the interior of an air purifier according to another embodiment of the present disclosure.

[0121] Referring to FIGS. 4 and 5, the air purifier (2000) includes a main body (110) forming an exterior, an intake port (111) for intake air from an indoor space, an outlet port (113) for exhausting the intake and purified air, a fan (141) for moving air so that the air intake into the intake port (111) is exhausted to the outlet port (113), and a deodorizing device (130) disposed between the intake port (111) and the outlet port (113). The deodorizing device (130) may be disposed adjacent to the intake port (111), for example. The deodorizing device (130) may be disposed upstream of the fan (141), for example. The interior of the main body (110) of the air purifier (2000) includes the deodorizing device (130), the fan (141), and the fan motor (143). A fan (141) is included to introduce indoor air into the main body (110) through the intake port (111). A fan motor (143) is included to drive the fan (141). By driving the fan (141) through the fan motor (143), indoor air is introduced into the main body (110) through the intake port (111). The air introduced into the intake port (111) passes through a deodorizing device (130), and odors in the air are removed through the deodorizing device (130). The deodorizing device (130) includes a deodorizing filter (not shown). Fig. 6 is a perspective view illustrating the exterior of an air conditioner according to one embodiment of the present disclosure. Fig. 7 is a cross-sectional view illustrating the interior of an air conditioner according to one embodiment of the present disclosure.

[0122] Referring to FIGS. 6 and 7, the air conditioner (4000) includes a main body (310) forming an exterior, an intake port (311) for intake of air from an indoor space, an exhaust port (313) for exhausting the intake and cooled air, a fan (341) for moving air so as to exhaust the air introduced into the intake port (311) to the exhaust port (313), a heat exchanger (350) for exchanging heat between the air introduced into the intake port (311) and a refrigerant, and a deodorizing device (330) disposed between the intake port (311) and the exhaust port (313). The deodorizing device (330) may be disposed, for example, adjacent to the intake port (311). The deodorizing device (330) may be disposed, for example, upstream of the heat exchanger (350). The deodorizing device (330) may be disposed, for example, upstream of the fan (341). Air drawn into the intake port (311) at the bottom of the main body (310) exchanges heat with the refrigerant of the heat exchanger (350) to be cooled, and is discharged through the discharge port (313) at the top of the main body (310). A fan (341) is arranged at the top, i.e., downstream, of the heat exchanger (350). The fan (341) is arranged surrounded by a duct (345). The fan (341) is driven by a drive motor (343). The fan (341) is connected to the shaft of the drive motor (343). The duct (345) surrounds the side of the fan (341), and the front of the fan (341) is open. The cooled air drawn into the front of the fan (341) rotates along the side of the fan (341) and moves to the open upper part of the duct (345). The cooled air moved to the open upper part of the duct (345) is discharged through the discharge port (313) at the top of the main body (310). The air flowing into the intake port (311) passes through the deodorizing device (330), and the odor in the air is removed through the deodorizing device (330). The deodorizing device (330) includes a deodorizing filter (not shown).

[0123] The deodorizing device (20) of the refrigerator of FIGS. 1 to 3, the deodorizing device (130) of the air purifier of FIGS. 4 to 5, and the deodorizing device (330) of the air conditioner of FIGS. 6 to 7 each include a deodorizing filter (not shown).

[0124] A deodorizing filter comprises a substrate; and a deodorizing film on a surface of the substrate. The deodorizing film comprises a deodorizing catalyst. The deodorizing filter contains δ-type MnO2 and CeO2, and has a structure in which CeO2 is coated with δ-type MnO2. Since CeO2 has a structure in which it is coated with δ-type MnO2, the deodorizing catalyst can have an increased specific surface area. As a result, the deodorizing performance of the deodorizing catalyst can be improved. In contrast, a simple combination of CeO2 and δ-type MnO2 can reduce the specific surface area of ​​the deodorizing catalyst because CeO2 is arranged on the surface as δ-type MnO2. As a result, the deodorizing performance of the deodorizing catalyst can be deteriorated. Since CeO2 has a structure in which it is coated with δ-type MnO2, the δ-type MnO2 is strongly anchored on the CeO2, so that oxygen transfer between the δ-type MnO2 and the CeO2 can be facilitated. As a result, the regeneration effect of δ-type MnO2 can be promoted, thereby improving the lifespan of the deodorizing catalyst.

[0125] <Configuration of the deodorizing filter according to the present embodiment>

[0126] (1) Deodorizing filter

[0127] The deodorizing filter of the present embodiment is installed in an air purifier, refrigerator, or air conditioner to adsorb and decompose components that cause odors, such as formaldehyde, ammonia, toluene, trimethylamine, and methyl mercaptan. Specifically, the deodorizing filter may be a honeycomb filter having a filter substrate having a honeycomb structure, as illustrated in Fig. 8, and a deodorizing film formed on the surface of the filter substrate to exhibit a deodorizing function. In addition, the deodorizing filter is not limited to a honeycomb filter, and may have any shape as long as a deodorizing film is formed on the surface of the substrate.

[0128] (2) Deodorizing film

[0129] The deodorizing film may be a thin film containing a particulate deodorizing catalyst and an inorganic binder for supporting the deodorizing catalyst on a filter substrate. The deodorizing catalyst of the present embodiment is a polar substance mainly composed of a metal oxide, and exhibits adsorption properties for polar substances among malodor molecules, such as formaldehyde, ammonia, trimethylamine, and methyl mercaptan. Furthermore, the deodorizing catalyst of the present embodiment has a decomposition function for the above-described polar substances without heating.

[0130] If the content of the deodorizing catalyst in the deodorizing film is too low, the deodorizing catalyst may become embedded in the inorganic binder, reducing its adsorption and decomposition capabilities. For example, the content of the deodorizing catalyst may be 50 wt% or more, or 80 wt% or more, based on 100 wt% of the total weight of the deodorizing film.

[0131] Meanwhile, if the content of the deodorizing catalyst in the deodorizing film is too high, the deodorizing catalyst may not be dispersed in the inorganic binder. For example, the content of the deodorizing catalyst may be 98 wt% or less, or 97 wt% or less, based on 100 wt% of the total weight of the deodorizing film.

[0132] The inorganic binder may be composed of, but is not limited to, colloidal silica, water glass, calcium silicate, alumina sol, titania sol, silicone oil, metal alkoxide, etc.

[0133] The deodorizing film may further contain activated carbon. Activated carbon can adsorb and retain non-polar substances that polar deodorizing catalysts have difficulty adsorbing. Non-polar substances may include, for example, toluene. In the deodorizing film, the activated carbon particles may be positioned adjacent to the deodorizing catalyst particles. For this purpose, rather than physically mixing the activated carbon with the δ-type MnO2 particles, as in the case of CeO2 particles, activated carbon coated with δ-type MnO2 through a crystallization method may be used.

[0134] If the activated carbon content is too low, non-polar substances may not be adsorbed and retained, leading to their re-release before decomposition. For example, the activated carbon content may be 5% by weight or more, or 10% by weight or more, based on the total weight of the deodorizing film being 100% by weight.

[0135] On the other hand, if the activated carbon content is too high, the amount of odor molecules that the deodorizing catalyst can adsorb decreases, which in turn reduces its ability to decompose odor molecules, potentially leading to destruction over time and the release of odors. For example, the activated carbon content may be 20% by weight or less, or 15% by weight or less, based on the total weight of the deodorizing film being 100% by weight.

[0136] The deodorizing film may contain one or more metal oxides selected from, for example, MgO, FeO, Fe2O3, ZrO2, CuO, NiO, Mn3O4, Co3O4, Al2O3, Y2O3, ZnO, MoO3, IrO2, WO3, W2O3, and TiO2. By containing such metal oxides in the deodorizing film, the types of decomposable odor molecules can be expanded, and the decomposition performance of odor molecules can be further improved.

[0137] (3) Deodorizing catalyst

[0138] The deodorizing catalyst is a particle-shaped deodorizing catalyst containing δ-type manganese dioxide (MnO2) and cerium oxide (CeO2) forming a layered structure.

[0139] In the deodorizing catalyst of the present embodiment, δ-type MnO2 is synthesized by crystal growth on the surface of CeO2 particles. Accordingly, the CeO2 particles form a structure in which they are covered with δ-type MnO2, and the CeO2 and δ-type MnO2 are strongly bonded to each other by the anchor effect. The CeO2 particles form a structure in which they are embedded in δ-type MnO2, and the CeO2 and δ-type MnO2 are strongly bonded to each other by the anchor effect.

[0140] The deodorizing catalyst of the present embodiment contains δ-type MnO2 having a layered structure with a large interlayer distance, so that it is easier to introduce odor molecules that cause odor than when it contains α-type MnO2 having a small tunnel-like pore diameter, and thus it is easier to adsorb these odor molecules. The deodorizing catalyst of the present embodiment can supply oxygen to the δ-type MnO2 responsible for the catalytic action by containing CeO2, and thus can regenerate the catalytic action of the δ-type MnO2. The deodorizing catalyst of the present embodiment has a structure in which CeO2 is covered with δ-type MnO2 (CeO2 is included in δ-type MnO2), and since these are in contact with each other by the anchor effect, it is easy to cause oxygen exchange from CeO2 to δ-type MnO2. The deodorizing catalyst of the present embodiment has a structure in which CeO2 is coated with δ-type MnO2, and since these are in contact with each other due to the anchor effect, it is difficult for CeO2 to fall off from δ-type MnO2, thereby promoting the regeneration of the catalytic function of δ-type MnO2 and maintaining the catalytic performance for a long period of time. Since δ-type MnO2 with high BET makes it easy for oxygen to be supplied to the inside of MnO2, by coating CeO2 with δ-type MnO2, oxygen exchange is possible not only on the surface of δ-type MnO2 but also on the inside, thereby promoting the regeneration of the catalytic action.

[0141] That CeO2 is coated with δ-type MnO2 can be confirmed by observation using SEM images and EDX mapping analysis performed on the deodorizing catalyst. An example thereof is shown in Figs. 9 and 10. As shown in Fig. 9, when the deodorizing catalyst of the present embodiment is observed using SEM images, only δ-type MnO2 can be confirmed, but CeO2 cannot be confirmed. On the other hand, when the observation point of Fig. 9 is analyzed by EDX mapping, the presence of CeO2 can be confirmed, as shown in Fig. 10. By comparing Figs. 9 and 10, it can be confirmed that CeO2 is coated with δ-type MnO2.

[0142] The deodorizing catalyst of the present embodiment, which has a structure in which CeO2 is coated with δ-type MnO2 (CeO2 is included in δ-type MnO2), can be obtained by adding CeO2 particles in advance during the synthesis process of δ-type MnO2 (crystal growth process of δ-type MnO2). Specifically, δ-type MnO2 can be obtained by dropping manganese sulfate (MnSO4) into a potassium permanganate (KMnO4) solution, and by adding CeO2 particles in advance to the potassium permanganate (KMnO4) solution before dropping manganese sulfate (MnSO4), crystals of δ-type MnO2 can be grown on the surfaces of the CeO2 particles. Accordingly, a deodorizing catalyst can be obtained in which CeO2 particles are coated with δ-type MnO2 (CeO2 is embedded in δ-type MnO2) and CeO2 and δ-type MnO2 are strongly bonded to each other by the anchor effect.

[0143] By growing δ-type MnO2 on the surface of CeO2 particles rather than physically mixing δ-type MnO2 particles and CeO2 particles, the porous structure of δ-type MnO2 becomes less likely to be damaged, and thus an excellent specific surface area can be obtained as described below.

[0144] The preferred content of each component, taking the total content of δ-type MnO2 and CeO2 in the catalyst as 100 wt%, is as follows.

[0145] If the content of δ-type MnO2 is too low, the surface area for adsorbing odor molecules may be insufficient, resulting in poor deodorizing and decomposition performance. For example, the content of δ-type MnO2 may be 90 wt% or more, or 94 wt% or more.

[0146] If the content of δ-type MnO2 is too high, oxygen supply by CeO2 may not be sufficient, and thus the catalytic function may not be sufficiently regenerated. For example, the content of δ-type MnO2 may be 99.5 wt% or less, or 96 wt% or less.

[0147] If the content of CeO2 is too low, oxygen supply to the δ-type MnO2 may not be sufficient, so that the catalytic function may not be sufficiently regenerated. For example, the content of CeO2 may be 0.5 wt% or more, or 4 wt% or more.

[0148] If the CeO2 content is too high, the surface area for adsorbing odor molecules may be insufficient, resulting in poor deodorizing and decomposition performance. For example, the CeO2 content may be 10 wt% or less, or 6 wt% or less.

[0149] The preferred average particle size of each particle in the deodorizing catalyst is as follows. The average particle size of each particle in the deodorizing catalyst can be measured from the particle size distribution by laser diffraction / scattering method.

[0150] If the average particle size of the CeO2-coated δ-type MnO2 catalyst is too large, it may be difficult to support the catalyst particles with an inorganic binder, which may cause powder to fall off during use. For example, the average particle size of the CeO2-coated δ-type MnO2 catalyst may be 20 μm or less, or 10 μm or less. For example, the average particle size of the CeO2-coated δ-type MnO2 catalyst may be 3 to 20 μm, or 3 to 10 μm.

[0151] If the average particle size of the δ-type MnO2 catalyst coated with CeO2 is too small, the surface area of ​​the catalyst will be covered by the inorganic binder as much as the surface area of ​​the catalyst increases, and thus sufficient deodorizing performance cannot be achieved. For example, the average particle size of the δ-type MnO2 particles may be 3 μm or more.

[0152] If the average particle size of CeO2 is too large, the contact area with δ-type MnO2 may be small, and sufficient oxygen supply performance may not be achieved. For example, the average particle size of the CeO2 particles may be 0.5 μm or less. For example, the average particle size of the CeO2 particles may be 0.01 to 0.5 μm.

[0153] The specific surface area of ​​the deodorizing catalyst is 250 m in BET value. 2 / g or more, 280m 2 / g or more, or 300m 2 / g or more. The BET value of the specific surface area can be measured from the gas adsorption amount by N2. The specific surface area of ​​the deodorizing catalyst is 250 m in BET value. 2 By making it more than / g, it can have a surface area sufficient for adsorption of odor molecules, and it can decompose odor molecules with high efficiency.

[0154] δ-type MnO2 may have a layered structure. The distance between adjacent layers in the layered structure may be, for example, 7 Å or more, or 7.2 Å or more.

[0155] Since the δ-type MnO2 has an interlayer spacing of 7 Å or more, formaldehyde having a size of about 5.2 Å, ammonia having a size of 3.3 Å, toluene having a size of 5.9 Å, trimethylamine having a size of 7 Å, and methyl mercaptan having a size of 4 Å can be easily adsorbed into the deodorizing catalyst and decomposed.

[0156] The deodorizing catalyst can be regenerated by ultraviolet light. For example, an additional ultraviolet light source capable of regenerating the deodorizing catalyst can be placed within the refrigerator.

[0157] Example

[0158] Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples, and modifications may be made within the scope of the above and later descriptions, all of which are included within the technical scope of the present invention.

[0159] (Experimental Example 1)

[0160] Deodorizing catalysts and deodorizing films were produced so as to have the mixing ratios shown in Table 1 below (Examples 1 to 4, Comparative Examples 1 to 5). In the mixing ratio column of Table 1, “MnO2:CeO2” represents the weight ratio of MnO2 and CeO2 in the deodorizing catalyst. “MnO2,” “CeO2,” and “activated carbon” represent the weight ratios of each component in the deodorizing film. The samples of Examples 1 to 4 and Comparative Examples 1 to 4 are deodorizing catalysts and deodorizing films containing δ-type MnO2, and the sample of Comparative Example 5 is a deodorizing catalyst and deodorizing film containing α-type MnO2. The samples of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained by growing δ-type MnO2 crystals on the surface of CeO2 particles by the above-described method, and the sample of Comparative Example 4 was obtained by physically mixing pre-prepared CeO2 particles and δ-type MnO2 particles using a mill or the like.

[0161] (Analysis by SEM-EDX)

[0162] The surface of the deodorizing catalyst powder of each obtained sample was observed by SEM (scanning electron microscope), and the state of each particle was confirmed by analysis by EDX mapping. In the deodorizing catalysts of Examples 1 to 4 and Comparative Examples 1 to 3 obtained by crystal growth of δ-type MnO2 on the surface of CeO2 particles, it was confirmed by EDX mapping that the CeO2 particles were embedded in δ-type MnO2, as shown in Fig. 10. Fig. 9 is an SEM image of the same field of view of the EDX mapping shown in Fig. 10, observing the surface of the deodorizing catalyst of Example 4.

[0163] Meanwhile, in the deodorizing catalyst of Comparative Example 4, which was obtained by physically mixing pre-prepared CeO2 particles and δ-type MnO2 particles using a mill or the like, it was confirmed that the CeO2 particles were not embedded in the δ-type MnO2, but were attached to the surface of the δ-type MnO2 particles, as shown in the SEM image of Fig. 11. This appearance is also evident in Fig. 12, which is an EDX mapping observation of the field of view of Fig. 11.

[0164] (Measurement of the mixture)

[0165] The mixing ratio of CeO2 and MnO2 in the deodorizing catalyst of each obtained sample and the mixing ratio of CeO2, MnO2 and activated carbon in the deodorizing film were measured by quantitative analysis of Mn and Ce using XPS (X-ray photoelectron spectroscopy) (KRATOS ULTRA2, Shimadzu Corporation). The mixing amount of activated carbon was estimated from the introduction amount.

[0166] (Measurement of BET value)

[0167] The specific surface area (BET value) of each sample was measured using a gas / vapor adsorption measuring device (BELSORP-max II, Microtrack Bell Co., Ltd.) by calculating the adsorption curve in the range of relative pressure p / p0 = 0.0 to 0.20 of the N2 adsorption isotherm measured at 298 K. (Reference: JIS Z 8830)

[0168] (Measurement of particle size distribution)

[0169] The particle size distribution of the δ-type MnO2 catalyst coated with CeO2 of each sample was measured by image observation using a laser diffraction particle size distribution measuring device (SALD-2300 manufactured by Shimadzu Corporation) and a scanning electron microscope (SEM) (JSM-IT800 manufactured by Nippon Electronics Co., Ltd.).

[0170] The deodorizing performance and lifespan of each obtained sample were evaluated. The evaluation method was as follows.

[0171] (Deodorization performance evaluation)

[0172] The deodorizing performance of air purifier filters against odor molecules (formaldehyde, ammonia, toluene) and refrigerator filters against odor molecules (trimethylamine, methyl mercaptan) was evaluated using honeycomb filters with a deodorizing film formed on the surface of each sample.

[0173] Specifically, a filter was installed in a 500 L chamber, and a predetermined amount of measurement gas was injected into the chamber, and then the deodorizing performance was measured using a detection tube for the measurement gas. For each odor molecule, the residual rate (%), which is the ratio of the concentration after 60 minutes to the concentration after 0 minutes (initial concentration), was calculated, and a residual rate of 20% or less was marked as “○”, over 20% but less than 60% as “△”, and over 60% as “×”. Samples that were evaluated as “△” or “×” for both the odor molecules targeted by the air purifier and the odor molecules targeted by the refrigerator were evaluated as “×” for their comprehensive deodorizing performance, and other samples were evaluated as “○” for their comprehensive deodorizing performance. The results are shown in Table 1.

[0174] (Life Assessment)

[0175] The service life of each sample was evaluated using a honeycomb filter having a deodorizing film formed on its surface. Specifically, the filter was installed in a 500 L chamber, a predetermined amount of measurement gas was injected into the chamber, and the deodorizing rate was measured for the first time using a detection tube for the measurement gas. After the test, ventilation was performed for 1 hour by operating a fan in the filter as a regeneration operation. This operation was considered 1 cycle, and this was performed 20 times. The service life was calculated as the ratio of the deodorizing rate (%) at the 20th time to the deodorizing rate (%) at the 1st time, and a value of 60% or more was marked as "○", a value of more than 40% but less than 60% was marked as "△", and a value of 40% or less was marked as "×". The results are shown in Table 1.

[0176] (Comprehensive judgment)

[0177] If both the deodorizing performance evaluation and the life evaluation were evaluated as “○,” the overall judgment was “○” (good). On the other hand, if either the deodorizing performance evaluation or the life evaluation was evaluated as “△” or “×,” the overall judgment was “×” (poor).

[0178]

[0179] As can be seen from the results in Table 1, CeO2 forms a structure in which δ-type MnO2 is included, and the average particle diameter of the catalyst having this structure is 20 μm or less, and additionally, the specific surface area is 250 m in BET value. 2 It was confirmed that the deodorizing filters (Examples 1 to 4) prepared using a deodorizing catalyst having a concentration of / g or more achieved excellent results in both the deodorizing performance evaluation and the lifespan evaluation. The deodorizing filter of Example 4 had an × score in the evaluation of deodorizing performance for toluene, which is because the deodorizing film did not contain activated carbon, a nonpolar substance.

[0180] Meanwhile, Comparative Examples 1 to 5 did not obtain excellent results in either or both of the deodorizing performance evaluation and the life evaluation.

[0181] Comparative Example 1 has a life evaluation of “×”. This is because the catalyst does not contain CeO2, and thus oxygen is not supplied to the δ-type MnO2 that adsorbs and decomposes the odor molecules.

[0182] Comparative Example 2 has a deodorizing performance evaluation of "×", which is because the content of δ-type MnO2 in the deodorizing catalyst is low, so the overall specific surface area (BET value) is 250 m 2 It was judged to be due to the fact that it was less than / g.

[0183] In Comparative Example 3, the particle size of the δ-type MnO2 in the manufactured catalyst was too large, which deteriorated the slurry dispersibility and prevented the formation of a deodorizing film on the surface of the filter.

[0184] Comparative Example 4 has a deodorizing performance evaluation of "×", which means that the porous structure of the δ-type MnO2 is destroyed by physically mixing the δ-type MnO2 particles and CeO2 particles, resulting in a specific surface area (BET value) of 250 m 2 It was thought that this was due to the fact that the δ-type MnO2 particles and CeO2 particles were lowered to below / g. Comparative Example 4 had a life evaluation of “×”, which was thought to be because the δ-type MnO2 particles and CeO2 particles were not firmly bonded when physically mixed, so that the CeO2 particles fell off from the MnO2 particles when slurried, making it impossible to maintain the catalytic activity effect by CeO2.

[0185] Comparative Example 5 has a deodorizing performance evaluation of “×”. This is thought to be because it is difficult to capture odor molecules by using α-type MnO2 having a tunnel-like structure with a small pore diameter.

[0186] In this experimental example, it was revealed that by using a δ-type MnO2 catalyst coated with CeO2, decomposition of several malodorous molecules (specifically, formaldehyde, ammonia, and trimethylamine) proceeds at room temperature without heating according to the reaction scheme shown in Fig. 13. By growing δ-type MnO2 crystals on CeO2 and making a catalyst in which CeO2 is supported on δ-type MnO2 (CeO2 is incorporated into δ-type MnO2), a new discovery was made regarding the decomposition principle of malodorous molecules (specifically, ammonia, toluene, trimethylamine, and methyl mercaptan), as shown in Fig. 14. Details are shown in Fig. 7.

[0187] (Experimental Example 2)

[0188] In Experimental Example 2, the effect of covering CeO2 with δ-type MnO2 on the deodorizing performance for HCHO was confirmed.

[0189] As illustrated in Fig. 15, two types of deodorizing catalyst samples with different manufacturing methods were prepared, and a deodorizing test using HCHO was performed on each of them. One deodorizing catalyst sample was prepared by crystallizing δ-type MnO2 on the surface of CeO2 particles (described as “bonding method”), and CeO2 was coated with δ-type MnO2. The other deodorizing catalyst sample was obtained by physically mixing CeO2 particles and δ-type MnO2 particles using a mill or the like (described as “blending method”), and CeO2 was not coated with δ-type MnO2. These two types of catalyst particle samples have the same specific surface area and the same weight ratio of CeO2 to δ-type MnO2. In addition, both deodorizing tests were performed at the same temperature (room temperature). More specific test conditions and material specifications are as described in Fig. 15.

[0190] As can be seen in Fig. 15, it was confirmed that by covering CeO2 with δ-type MnO2 under the conditions of the same specific surface area, the same weight ratio of CeO2 and δ-type MnO2, and the same test temperature, the oxygen supply efficiency by CeO2 was improved, and the deodorization rate and HCHO decomposition action exhibited high performance even after repeated tests.

[0191] (Experimental Example 3)

[0192] In Experimental Example 3, the regeneration promotion performance by irradiating the catalyst particles with UV-C was confirmed.

[0193] The decomposition promotion effect by light irradiation was confirmed using a honeycomb filter having a deodorizing film of the present invention formed on the surface. For example, the deodorizing performance of a refrigerator filter for a target odor molecule (trimethylamine) was repeatedly evaluated using a UV-C lamp (Sankyo Denki, 8W). The filter was installed in a 100 L chamber, a predetermined amount of measurement gas was injected into the chamber, and the deodorizing performance was measured using a detection tube for the measurement gas. The deodorizing rate (%) was calculated from the ratio of the concentration after 30 minutes to the concentration after 0 minutes (initial concentration) for trimethylamine, and the deodorizing rate when repeated evaluations were performed was plotted. Detailed evaluation conditions and test results are shown in Fig. 16.

[0194] As shown in Fig. 16, the deodorization rate was compared with and without UV-C irradiation for 1 hour after the performance evaluation (fan stop is a common condition). In the evaluation where UV-C irradiation was performed for 1 hour, the deodorization performance tended to be maintained even when the deodorization rate was repeated, and it was confirmed that the performance tended to recover as decomposition was promoted.

[0195] The current considerations on the principle of promoting catalyst regeneration by UV light irradiation are shown in Fig. 17. Since δ-type MnO2 has a narrower band gap than other structures (α, β, γ), it has high activity as a photocatalyst. In other words, since δ-type MnO2 also has high photocatalytic activity, it is possible to generate ·OH by irradiating UV. As shown in Equation 1 of Fig. 17, the generated ·OH reacts with TMA and undergoes decomposition. Since the oxidative decomposition reaction at room temperature shown in Equation 2 also proceeds in the same manner, it is thought that the decomposition of TMA (trimethylamine) was promoted.

[0196] According to an embodiment of the present invention, a refrigerator is provided that can exhibit excellent deodorizing performance over a long period of time in a deodorizing filter used in the refrigerator.

[0197] According to an embodiment of the present invention, an air purifier is provided that can exhibit excellent deodorizing performance for a long period of time in a deodorizing filter used in the air purifier.

[0198] According to one embodiment, a home appliance is provided that can exhibit excellent deodorizing performance for a long period of time in a deodorizing filter used in the home appliance.

Claims

1. Internal cavity forming a storage room; A body including an external wound on the inner surface of the above; a door configured to open and close the storage room; and Includes a deodorizing device placed inside the above storage room, The above deodorizing device includes a deodorizing filter, The above deodorizing filter comprises a substrate; and a deodorizing film on the surface of the substrate, The above deodorizing film contains a deodorizing catalyst, and the above deodorizing catalyst Contains δ-type MnO2 and CeO2, CeO2 forms a structure covered with δ-type MnO2, The average particle size of δ-type MnO2 is less than 20 μm, The specific surface area is 250m in BET value. 2 / g or more, refrigerator.

2. In paragraph 1, The content of δ-type MnO2 is 90 wt% or more and 99.5 wt% or less, A refrigerator having a CeO2 content of 0.5 wt% or more and 10 wt% or less.

3. In paragraph 1, A refrigerator having an average particle size of δ-type MnO2 coated with CeO2 of 20 μm or less.

4. In paragraph 1, The above δ-type MnO2 has a layered structure, A refrigerator, wherein the distance between adjacent layers included in the above layered structure is 7 ㅕ or more.

5. In paragraph 1, A refrigerator, wherein the above deodorizing film further contains an inorganic binder.

6. In paragraph 1, A refrigerator wherein the above deodorizing film further contains activated carbon.

7. In paragraph 1, A refrigerator, wherein the above deodorizing film further contains at least one selected from MgO, FeO, Fe2O3, ZrO2, CuO, NiO, Mn3O4, Co3O4, Al2O3, Y2O3, ZnO, MoO3, IrO2, WO3, W2O3, and TiO2.

8. In paragraph 1, A refrigerator having a honeycomb structure as described above.

9. In paragraph 1, A refrigerator further comprising an ultraviolet light source for regenerating the deodorizing catalyst.

10. A main body having an intake port and an exhaust port; A fan that moves the air drawn into the intake port so as to discharge the air through the exhaust port; A deodorizing device is included, which is arranged between the suction port and the discharge port. The above deodorizing device includes a deodorizing filter, The above deodorizing filter comprises a substrate; and a deodorizing film on the surface of the substrate, The above deodorizing film contains a deodorizing catalyst, and the above deodorizing catalyst Contains δ-type MnO2 and CeO2, CeO2 forms a structure covered with δ-type MnO2, The average particle size of δ-type MnO2 is less than 20 μm, The specific surface area is 250m in BET value. 2 / g or higher, air purifier.

11. In clause 10, The content of δ-type MnO2 is 90 wt% or more and 99.5 wt% or less, An air purifier having a CeO2 content of 0.5 wt% or more and 10 wt% or less.

12. In paragraph 10, An air purifier having an average particle size of δ-type MnO2 coated with CeO2 of 20 μm or less.

13. In paragraph 10, The above deodorizing film Contains more weapon binders or Contains more activated carbon or An air purifier further containing at least one selected from MgO, FeO, Fe2O3, ZrO2, CuO, NiO, Mn3O4, Co3O4, Al2O3, Y2O3, ZnO, MoO3, IrO2, WO3, W2O3, and TiO2.

14. In paragraph 10, An air purifier having a honeycomb structure as described above.

15. A main body having an intake port and an exhaust port; A fan that moves the air drawn into the intake port so as to discharge the air through the exhaust port; A heat exchanger that exchanges heat between air and refrigerant flowing into the above intake port; A deodorizing device is included, which is arranged between the suction port and the discharge port. The above deodorizing device includes a deodorizing filter, The above deodorizing filter comprises a substrate; and a deodorizing film on the surface of the substrate, The above deodorizing film contains a deodorizing catalyst, and the above deodorizing catalyst Contains δ-type MnO2 and CeO2, CeO2 forms a structure covered with δ-type MnO2, The average particle size of δ-type MnO2 is less than 20 μm, The specific surface area is 250m in BET value. 2 / g or higher, home appliances.

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