Supported Cu < + > bactericidal material as well as preparation method and application thereof

Abstract

The invention provides a supported Cu < + > bactericidal material. The supported Cu < + > bactericidal material comprises a carrier and a Cu < + > compound supported on the surface of the carrier, the mass of Cu < + > in the Cu < + > compound accounts for 4-12% of the mass of the carrier; the specific surface area of the carrier is 80m < 2 > / g-1000m < 2 > / g, and the pore diameter is 0.4 nm-18nm. According to the invention, the Cu < + > compound with bactericidal activity is loaded on the surface of the carrier with a specific structure, so that the dispersibility of the bactericidal active component of the Cu < + > compound is improved, and the bactericidal performance of the loaded Cu < + > bactericidal material is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of bactericidal materials, specifically to the field of inorganic bactericidal materials, and in particular to a Cu3P / Al2O3 bactericidal material and a preparation method and application thereof. Background Art

[0002] Pathogenic microorganisms include bacteria, fungi, viruses, etc., which can induce a variety of diseases and endanger human health. At present, commonly used inorganic bactericidal materials include Ag2O, CuO, Cu2O, ZnO, TiO2, CaO, MgO, etc. and their composite materials. Among them, the cost of copper materials is lower than that of silver materials, and the bactericidal activity of monovalent copper materials is often better than that of divalent copper materials.

[0003] CN116920088A discloses a mesoporous polydopamine / cuprous sulfide-polyethyleneimine nanocomposite material and its preparation method and application. The nanocomposite material is composed of mesoporous polydopamine, cuprous sulfide and polyethyleneimine, wherein the mesoporous polydopamine is prepared by in-situ polymerization of dopamine-copper ion chelate, cuprous sulfide is loaded inside and on the surface of polydopamine, and polyethyleneimine is loaded on the surface of mesoporous polydopamine / cuprous sulfide. The nanocomposite material can achieve high antibacterial activity at low concentrations when used as an antibacterial agent, but the nanocomposite material can only function under light.

[0004] CN105123753A discloses a nano cuprous oxide fungicide composition for in-situ reduction of lignin, which is obtained by mixing 10-40 parts of nano cuprous oxide powder, 0.1-15 parts of surfactant, 5-30 parts of dispersant and 30-70 parts of water, and grinding for 1-4 hours. The product prepared by the invention has a good fungicide effect, but the preparation method is complicated and is not suitable for large-scale industrial applications.

[0005] CN119234798A discloses a method for preparing a copper-based nanoparticle / attapulgite composite antibacterial material using red peony root extract, wherein active substances are extracted from the Chinese medicinal material red peony root as a reducing agent and a stabilizer, and attapulgite is used as a carrier to prepare the copper-based nanoparticle / attapulgite composite antibacterial material through a hydrothermal reaction. The nanocomposite material prepared by the invention has high antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) and extended-spectrum β-lactamase-producing Escherichia coli (ESBLs-E.coli), but its high antibacterial activity needs to rely on photocatalysis, and the preparation of the composite antibacterial material is complicated.

[0006] Therefore, it is of great significance to develop a loaded monovalent copper bactericidal material with a simple preparation process and which can achieve efficient bactericidal effect without relying on external auxiliary conditions. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention aims to provide a supported Cu + Bactericidal material and its preparation method and application. The present invention uses Cu with bactericidal activity + The compound is loaded onto the surface of a carrier with a specific structure, which increases the Cu + The dispersibility of the bactericidal active components of the compound was improved, thereby improving the supported Cu + Bactericidal properties of bactericidal materials.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a supported Cu + Bactericidal material, the supported Cu + The bactericidal material includes a carrier and Cu loaded on the surface of the carrier. + Compounds;

[0010] The Cu + Cu in compounds + The mass of the carrier accounts for 4%-12% of the mass of the carrier;

[0011] The specific surface area of ​​the carrier is 80 m 2 / g-1000m 2 / g, pore size is 0.4nm-18nm.

[0012] The present invention provides a supported Cu + Sterilization material, Cu with bactericidal activity + The compound is loaded onto the surface of a carrier with a specific surface area and pore size, which increases the Cu + The dispersibility of the compound avoids the + The reduction of bactericidal performance caused by compound agglomeration is conducive to fully utilizing Cu + bactericidal properties; and the supported Cu provided by the present invention + The bactericidal material does not require auxiliary means such as light, electricity or heat, and can achieve excellent bactericidal performance at a lower loading amount.

[0013] The supported Cu + In sterilization materials, Cu + Cu in compounds + The mass of Cu accounts for 4%-12% of the mass of the carrier, for example, it can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12%, including but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable. + Cu in compounds + If the mass ratio of Cu is too large, it will lead to +The compound is poorly dispersed and the particle size is too large, which is not conducive to fully utilizing Cu + The bactericidal properties of the compounds, if Cu + Cu in compounds + If the mass proportion is too small, the active components are too few and the bactericidal effect is poor.

[0014] The present invention specifically selects the specific surface area and pore size of the carrier, and selects a specific surface area of ​​80m 2 / g-1000m 2 / g, the carrier with pore size of 0.4nm-18nm is more conducive to Cu + The compound is evenly dispersed and its bactericidal properties are fully exerted.

[0015] In the present invention, the specific surface area of ​​the carrier is 80m 2 / g-1000m 2 / g, for example, it can be 80m 2 / g, 90m 2 / g、100m 2 / g, 200m 2 / g、300m 2 / g, 400m 2 / g、500m 2 / g, 600m 2 / g、700m 2 / g、800m 2 / g、900m 2 / g or 1000m 2 / g, and a pore size of 0.4nm-18nm, for example, 0.4nm, 0.6nm, 0.8nm, 1.0nm, 2.0nm, 4.0nm, 5.0nm, 6.0nm, 8.0nm, 10.0nm, 12.0nm, 14.0nm, 16.0nm or 18.0nm. The specific surface area and pore size of the above-mentioned carrier include but are not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0016] Preferably, the specific surface area of ​​the carrier is 200 m 2 / g-800m 2 / g, pore size is 5nm-12nm.

[0017] The present invention identifies the specific surface area and pore size of the carrier, and further preferably the specific surface area of ​​the carrier is 200m 2 / g-800m 2 / g, pore size is 5nm-12nm. If the specific surface area of ​​the carrier is too small or the pore size is too small, it is not conducive to Cu + The dispersion of the compound leads to Cu +The compound particle size is large, the reduction degree is low, and the Cu distributed on the surface of the material + less.

[0018] Preferably, the Cu + The particle size of the compound is 1nm-20nm, for example, it can be 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm or 20nm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0019] Preferably, the Cu + When the particle size of the compound is 8nm-12nm, the supported Cu + Sterilization materials have a more excellent sterilization effect.

[0020] Preferably, the Cu + Compounds include Cu3P.

[0021] In the present invention, Cu3P is selected as the active component of the bactericidal material, and electron transfer occurs between Cu and P, making the chemical properties of Cu3P more stable and able to better play the role of Cu + Activated oxygen generates reactive oxygen species such as superoxide radicals, thereby increasing bactericidal activity.

[0022] Preferably, the carrier comprises any one of Al2O3, SiO2, ZrO2 or molecular sieves or a combination of at least two thereof. Typical but non-limiting combinations include a combination of Al2O3 and SiO2, a combination of ZrO2 and molecular sieves, a combination of SiO2 and ZrO2, or a combination of molecular sieves and Al2O3.

[0023] Preferably, the molecular sieve comprises any one of MCM-41 molecular sieve, SBA-15 molecular sieve, X-type molecular sieve, Y-type molecular sieve, ZSM-5 molecular sieve or Beta molecular sieve, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of MCM-41 molecular sieve and SBA-15 molecular sieve, a combination of X-type molecular sieve and Y-type molecular sieve, a combination of ZSM-5 molecular sieve and Beta molecular sieve, a combination of SBA-15 molecular sieve and X-type molecular sieve, a combination of Y-type molecular sieve and ZSM-5 molecular sieve, or a combination of Beta molecular sieve and MCM-41 molecular sieve.

[0024] Preferably, when the carrier is any one of Al2O3, SBA-15 molecular sieve or MCM-41 molecular sieve or a combination of at least two of them, the supported Cu + Sterilization materials have a more excellent sterilization effect.

[0025] The second invention provides a supported Cu + A method for preparing a bactericidal material, the preparation method comprising:

[0026] The copper salt is dissolved in the dispersion of the carrier, dried, and calcined to obtain the Cu-loaded precursor; the Cu-loaded precursor is subjected to reduction heat treatment to prepare the loaded Cu + Sterilization materials;

[0027] The mass of Cu in the copper salt is 4%-12% of the mass of the carrier.

[0028] The preparation method provided by the present invention first loads Cu on the surface of a carrier with a specific structure, and then performs a reduction heat treatment to ensure that Cu + The compound is evenly distributed on the surface of the carrier, increasing the Cu + The dispersibility of the compound can give full play to the Cu + The bactericidal properties of the compounds were improved, and the prepared supported Cu + The bactericidal effect of bactericidal materials.

[0029] The mass of Cu in the copper salt is 4%-12% of the mass of the carrier, for example, it can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12%, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Preferably, the reduction heat treatment comprises placing the reducing agent and the Cu-supported precursor in an inert atmosphere, and calcining to prepare the supported Cu + Sterilization materials.

[0031] Preferably, the reducing agent comprises hypophosphite.

[0032] Preferably, the hypophosphite comprises any one of sodium hypophosphite, potassium hypophosphite or calcium hypophosphite or a combination of at least two thereof, and typical but non-limiting combinations include a combination of sodium hypophosphite and potassium hypophosphite, a combination of calcium hypophosphite and sodium hypophosphite, or a combination of potassium hypophosphite and calcium hypophosphite.

[0033] The present invention uses hypophosphite as a reducing agent. The hypophosphite decomposes and releases PH3 during the heat treatment process, and reacts with Cu in the Cu-loaded precursor to obtain Cu3P-loaded Cu. + Compared with other phosphorus sources, such as phosphites, the hypophosphites in the present invention are more conducive to producing PH3 at a lower temperature.

[0034] Preferably, the copper salt comprises any one of copper sulfate, copper chloride, copper nitrate or copper acetate, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of copper sulfate and copper chloride, a combination of copper nitrate and copper acetate, a combination of copper chloride and copper nitrate, or a combination of copper acetate and copper sulfate.

[0035] In the preparation method provided by the present invention, the reduction heat treatment only requires placing the reducing agent and the Cu-loaded precursor in an inert atmosphere for heat treatment, and the preparation process is simple and easy to realize industrial application.

[0036] Preferably, the reduction heat treatment process further comprises uniformly mixing the Cu-loaded precursor with the reducing component before placing the Cu-loaded precursor and the hypophosphite in an inert atmosphere.

[0037] Preferably, the molar ratio of P in the hypophosphite to Cu in the Cu-loaded precursor is (2-10):1, for example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] Preferably, the reduction heat treatment process further includes placing the hypophosphite at the upstream end of the inert gas introduction direction, and placing the Cu-loaded precursor at the downstream end of the inert gas introduction direction.

[0039] The upstream end and the downstream end of the inert atmosphere introduction direction in the present invention refer to the inert atmosphere introduction path. The position reached by the inert atmosphere first is defined as the upstream end, and the position reached later is defined as the downstream end. During the phosphating process, the inert atmosphere first reaches the position of the hypophosphite at the upstream end, and the PH3 gas generated by the decomposition of the hypophosphite reaches the position of the Cu-loaded precursor at the downstream end under the transportation of the inert atmosphere. The PH3 gas reacts with Cu to obtain Cu3P, and the Cu3P-loaded Cu is prepared. + Sterilization materials.

[0040] During the phosphating process of the present invention, the temperature of the reduction heat treatment affects the concentration of PH3. If the temperature of the reduction heat treatment is too low, the concentration of PH3 is low, which is not conducive to the formation of Cu3P; if the temperature of the reduction heat treatment is too high, PH3 will decompose, which is not conducive to the formation of Cu3P.

[0041] Preferably, during the reduction heat treatment process, the temperature of the reduction heat treatment is 250°C-450°C, for example, it can be 250°C, 300°C, 350°C, 400°C or 450°C, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0042] In the reduction heat treatment process of the present invention, the time of the reduction heat treatment affects the generation of Cu3P. If the time of the reduction heat treatment is too long, the dispersion of Cu3P is reduced. If the time of the reduction heat treatment is too short, it is not conducive to the generation of Cu3P.

[0043] Preferably, during the reduction heat treatment process, the reduction heat treatment time is 1h-5h, for example, 1h, 2h, 3h, 4h or 5h, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] Preferably, the inert gas in the inert atmosphere includes nitrogen and / or noble gas.

[0045] Preferably, the inert gas comprises argon and / or helium.

[0046] Preferably, the drying temperature is 60°C-120°C, for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0047] In the present invention, the time and manner of drying are not particularly limited. The purpose is to completely remove the solvent. The drying method may be, for example, rotary evaporation.

[0048] In the present invention, the temperature of calcining the Cu / Al2O3 precursor affects the dispersion and particle size of Cu in the prepared Cu / Al2O3. If the calcination temperature is too high, the particle size of Cu is too large. If the calcination temperature is too low, the stability of Cu / Al2O3 is poor.

[0049] Preferably, the calcination temperature is 400°C-600°C, for example, 400°C, 450°C, 500°C, 550°C or 600°C, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0050] Preferably, the calcination time is 2 h-6 h, for example, 2, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h or 6 h, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0051] In a third aspect, the present invention provides a supported Cu + Application of bactericidal materials, the supported Cu + Sterilization materials are used in the field of sterilization of pathogenic microorganisms.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] (1) The present invention uses Cu with bactericidal activity + The compound is loaded onto the surface of a carrier with a specific structure, which increases the Cu + The dispersibility of the compound avoids the + The bactericidal performance of the compound agglomeration is reduced, and the supported Cu + The bactericidal material does not require auxiliary means such as light, electricity or heat, and can achieve excellent bactericidal performance at a lower loading amount.

[0054] (2) The preparation method provided by the present invention first loads Cu on the surface of the carrier, and then performs a reduction heat treatment to ensure that Cu + The compound is evenly distributed on the surface of the carrier, increasing the Cu + The dispersibility of the compound can give full play to the Cu + The bactericidal properties of the compounds were improved, and the prepared supported Cu + The invention provides a simple preparation process and is easy to industrialize and apply. DETAILED DESCRIPTION

[0055] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0056] Example 1

[0057] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0058] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0059] The supported Cu + The preparation method of the sterilization material comprises:

[0060] (1) Preparation of Cu-loaded precursor: Dissolve copper nitrate in a dispersion of an Al2O3 carrier, the mass of Cu in the copper nitrate accounting for 8% of the mass of the Al2O3 carrier. Stir at 20°C for 1 h, rotary evaporate at 90°C and dry, and calcine to obtain a Cu-loaded precursor. The calcination temperature is 550°C and the calcination time is 4 h.

[0061] (2) Reduction heat treatment: The Cu-loaded precursor prepared in step (1) was mixed with sodium hypophosphite and subjected to heat treatment in a nitrogen atmosphere. The molar ratio of P in the sodium hypophosphite to Cu in the Cu-loaded precursor was 2:1. The temperature of the reduction heat treatment was 300° C. and the time of the reduction heat treatment was 3 h. + Sterilization materials.

[0062] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 9nm.

[0063] Example 2

[0064] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0065] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0066] The supported Cu + The preparation method of the sterilization material comprises:

[0067] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0068] (2) Reduction heat treatment: The same as in Example 1 except that the temperature of the reduction heat treatment is 400°C.

[0069] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 9.3nm.

[0070] Example 3

[0071] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0072] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0073] The supported Cu + The preparation method of the sterilization material comprises:

[0074] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0075] (2) Reduction heat treatment: The reduction heat treatment was carried out in the same manner as in Example 1 except that the time for the reduction heat treatment was 1 h.

[0076] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 8.7nm.

[0077] Example 4

[0078] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises a SiO2 carrier and Cu3P loaded on the surface of the SiO2 carrier; the mass of Cu in the Cu3P accounts for 4% of the mass of the SiO2 carrier.

[0079] The specific surface area of ​​the SiO2 carrier used in this example is 210 m 2 / g, pore size is 10nm.

[0080] The supported Cu + The preparation method of the sterilization material comprises:

[0081] (1) Preparation of Cu-loaded precursor: Dissolve cupric chloride in a dispersion of SiO2 carrier, the mass of Cu in the cupric chloride accounting for 4% of the mass of SiO2 carrier, stir at 20°C for 1 h, dry by rotary evaporation at 60°C, and calcine to obtain a Cu-loaded precursor at a calcination temperature of 400°C for 2 h.

[0082] (2) Reduction heat treatment: The Cu-loaded precursor prepared in step (1) was mixed with potassium hypophosphite and subjected to heat treatment in an argon atmosphere. The molar ratio of P in the potassium hypophosphite to Cu in the Cu-loaded precursor was 5:1. The heat treatment temperature was 250° C. and the heat treatment time was 1 h. The supported Cu was prepared. + Sterilization materials.

[0083] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 11.5nm.

[0084] Example 5

[0085] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an MCM-41 molecular sieve carrier and Cu3P loaded on the surface of the MCM-41 molecular sieve carrier; the mass of Cu in the Cu3P accounts for 12% of the mass of the MCM-41 molecular sieve carrier.

[0086] The specific surface area of ​​the MCM-41 molecular sieve carrier used in this example is 800 m 2 / g, pore size is 5nm.

[0087] The supported Cu + The preparation method of the sterilization material comprises:

[0088] (1) Preparation of Cu-loaded precursor: Dissolve cupric acetate in a dispersion of an MCM-41 molecular sieve carrier, wherein the mass of Cu in the cupric acetate accounts for 12% of the mass of the MCM-41 molecular sieve carrier. Stir at 20° C. for 1 h, perform rotary evaporation at 120° C., dry, and calcine to obtain a Cu-loaded precursor. The calcination temperature is 600° C., and the calcination time is 6 h.

[0089] (2) Reduction heat treatment: The Cu-loaded precursor and calcium hypophosphite prepared in step (1) are placed in a helium atmosphere for heat treatment, wherein the calcium hypophosphite is located at the upstream end of the helium atmosphere introduction direction, and the Cu-loaded precursor is located at the downstream end of the helium atmosphere introduction direction, and the molar ratio of P in the calcium hypophosphite to Cu in the Cu-loaded precursor is 10:1. The heat treatment temperature is 450° C. and the heat treatment time is 5 h. + Sterilization materials.

[0090] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 8nm.

[0091] Example 6

[0092] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The specific surface area of ​​the Al2O3 carrier used in the sterilization material is 190m 2 / g, and the pore diameter is 4nm, and the rest is the same as in Example 1.

[0093] The supported Cu + The preparation method of the sterilization material comprises:

[0094] (1) Preparation of Cu-supported precursor: The specific surface area of ​​the Al2O3 support is 190 m 2 / g, and the pore diameter is 4nm, and the rest is the same as in Example 1.

[0095] (2) Reduction heat treatment: same as in Example 1.

[0096] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 20nm.

[0097] Example 7

[0098] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The specific surface area of ​​the Al2O3 carrier used in the sterilization material is 900m 2 / g, and the pore diameter is 0.8nm, and the rest is the same as in Example 1.

[0099] The supported Cu + The preparation method of the sterilization material comprises:

[0100] (1) Preparation of Cu-supported precursor: The specific surface area of ​​the Al2O3 support is 900 m 2 / g, and the pore diameter is 0.8nm, and the rest is the same as in Example 1.

[0101] (2) Reduction heat treatment: same as in Example 1.

[0102] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 15nm.

[0103] Example 8

[0104] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0105] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0106] The supported Cu + The preparation method of the sterilization material comprises:

[0107] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0108] (2) Reduction heat treatment: The same as in Example 1 except that the molar ratio of P in sodium hypophosphite to Cu in Cu / Al2O3 is 1:1.

[0109] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 9.2nm.

[0110] Example 9

[0111] This embodiment provides a supported Cu + Bactericidal material, the supported Cu +The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0112] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0113] The supported Cu + The preparation method of the sterilization material comprises:

[0114] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0115] (2) Reduction heat treatment: The same as in Example 1 except that the temperature of the reduction heat treatment is 200°C.

[0116] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 9.1nm.

[0117] Example 10

[0118] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0119] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0120] The supported Cu + The preparation method of the sterilization material comprises:

[0121] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0122] (2) Except that the temperature of the reduction heat treatment is 550°C, the rest is the same as in Example 1.

[0123] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 9.6nm.

[0124] Embodiment 11

[0125] This embodiment provides a supported Cu + Bactericidal material, the supported Cu +The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0126] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0127] The supported Cu + The preparation method of the sterilization material comprises:

[0128] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0129] (2) Reduction heat treatment: The same as in Example 1 except that the reduction heat treatment time was 0.5 h.

[0130] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 8.5nm.

[0131] Example 12

[0132] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0133] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0134] The supported Cu + The preparation method of the sterilization material comprises:

[0135] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0136] (2) Reduction heat treatment: The same as in Example 1 except that the reduction heat treatment time is 6 h.

[0137] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 9.5nm.

[0138] Embodiment 13

[0139] This embodiment provides a supported Cu + Bactericidal material, the supported Cu +The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0140] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0141] The supported Cu + The preparation method of the sterilization material comprises:

[0142] (1) Preparation of Cu-supported precursor: The same procedures as in Example 1 except that the calcination temperature was 300°C.

[0143] (2) Reduction heat treatment: same as in Example 1.

[0144] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 8nm.

[0145] Embodiment 14

[0146] This embodiment provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material comprises an Al2O3 carrier and Cu3P loaded on the surface of the Al2O3 carrier; the mass of Cu in the Cu3P accounts for 8% of the mass of the Al2O3 carrier.

[0147] The specific surface area of ​​the Al2O3 carrier used in this example is 300m 2 / g, pore size is 12nm.

[0148] The supported Cu + The preparation method of the sterilization material comprises:

[0149] (1) Preparation of Cu-supported precursor: The same procedures as in Example 1 except that the calcination temperature was 700°C.

[0150] (3) Reduction heat treatment: same as in Example 1.

[0151] The supported Cu prepared in this example + In the bactericidal material, the particle size of Cu3P is 11nm.

[0152] Comparative Example 1

[0153] This comparative example provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material is the same as that in Example 1 except that the mass of Cu in Cu3P accounts for 2% of the mass of the Al2O3 carrier.

[0154] The supported Cu + The preparation method of the sterilization material comprises:

[0155] (1) Preparation of Cu-supported precursor: The same procedures as in Example 1 were followed except that the mass of Cu in copper nitrate accounted for 2% of the mass of the Al2O3 support.

[0156] (2) Reduction heat treatment: same as in Example 1.

[0157] The supported Cu prepared in this comparative example + In the bactericidal material, the particle size of Cu3P is 30nm.

[0158] Comparative Example 2

[0159] This comparative example provides a supported Cu + Bactericidal material, the supported Cu + The sterilization material is the same as that in Example 1 except that the mass of Cu in Cu3P accounts for 15% of the mass of the Al2O3 carrier.

[0160] The supported Cu + The preparation method of the sterilization material comprises:

[0161] (1) Preparation of Cu-supported precursor: The same procedures as in Example 1 were followed except that the mass of Cu in copper nitrate accounted for 15% of the mass of the Al2O3 support.

[0162] (2) Reduction heat treatment: same as in Example 1.

[0163] The supported Cu prepared in this comparative example + In the bactericidal material, the particle size of Cu3P is 22nm.

[0164] Comparative Example 3

[0165] This comparative example provides a supported Cu + Bactericidal material, the supported Cu + The specific surface area of ​​the sterilization material except Al2O3 carrier is 65m 2 / g, and the pore diameter is 5nm, and the rest is the same as in Example 1.

[0166] The supported Cu + The preparation method of the sterilization material comprises:

[0167] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0168] (2) Reduction heat treatment: same as in Example 1.

[0169] The supported Cu prepared in this comparative example + In the bactericidal material, the particle size of Cu3P is 50nm.

[0170] Comparative Example 4

[0171] This comparative example provides a supported Cu + Bactericidal material, the supported Cu + The specific surface area of ​​the sterilization material except Al2O3 carrier is 500m 2 / g, and the pore diameter is 2nm, and the rest is the same as in Example 1.

[0172] The supported Cu + The preparation method of the sterilization material comprises:

[0173] (1) Preparation of Cu-loaded precursor: Same as Example 1.

[0174] (2) Reduction heat treatment: same as in Example 1.

[0175] The supported Cu prepared in this comparative example + In the bactericidal material, the particle size of Cu3P is 19nm.

[0176] Comparative Example 5

[0177] This comparative example provides a Cu3P bactericidal material, and the preparation method of the Cu3P bactericidal material comprises:

[0178] (1) Preparation of Cu precursor: Calcination of copper nitrate to obtain a Cu precursor at a temperature of 550° C. for 4 h.

[0179] (2) Reduction heat treatment: The Cu precursor prepared in step (1) is mixed with sodium hypophosphite and subjected to heat treatment in a nitrogen atmosphere. The molar ratio of P in the sodium hypophosphite to Cu in the Cu precursor is 1:3. The temperature of the reduction heat treatment is 300°C and the time of the reduction heat treatment is 3 hours to prepare the Cu3P sterilization material.

[0180] In the supported Cu3P bactericidal material prepared in this comparative example, the particle size of Cu3P is 200nm.

[0181] Comparative Example 6

[0182] This comparative example provides a supported Cu 2+ The bactericidal material comprises an Al2O3 carrier and Cu loaded on the surface of the Al2O3 carrier. 2+ ; The Cu 2+ The mass of Cu accounts for 8% of the mass of Al2O3 support. 2+ The preparation method of the loaded sterilization material comprises:

[0183] Dissolve copper nitrate in the dispersion of Al2O3 carrier, the mass of Cu in copper nitrate accounts for 8% of the mass of Al2O3 carrier, stir at 20℃ for 1h, rotary evaporate at 90℃ and dry, calcine to obtain CuO loaded sterilization material, the calcination temperature is 550℃, and the calcination time is 4h.

[0184] The specific surface area of ​​the Al2O3 carrier used in this comparative example is 300m 2 / g, pore size is 12nm.

[0185] The supported Cu prepared in this comparative example 2+ In the bactericidal material, the particle size of CuO is 8.9 nm.

[0186] Performance Test:

[0187] The bactericidal performance test was performed on the bactericidal materials provided in all the embodiments of the present invention and the comparative examples.

[0188] The test conditions are:

[0189] The initial concentration of E. coli was 10 7 ~10 8 cfu / mL, calculated based on the mass of Cu in the bactericidal material, the concentration is 50μg / mL. After the bactericidal material was added to the E. coli solution for 30 minutes, 0.5mL of the solution was taken out, diluted multiple times by 10-fold dilution method, and cultured in a 37℃ incubator for 24 hours. The test results are shown in Table 1

[0190] Table 1

[0191]

[0192]

[0193] According to the test results of Examples 1 to 12 of the present invention, the present invention loads the bactericidal active Cu3P onto the surface of a carrier with a specific specific surface area and pore size according to a specific loading amount, which significantly improves the dispersibility of the bactericidal active component of Cu3P, thereby improving the Cu + Bactericidal properties of bactericidal materials.

[0194] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A supported Cu + A bactericidal material, characterized in that The supported Cu + The bactericidal material includes a carrier and Cu loaded on the surface of the carrier. + Compounds; The Cu + Cu in compounds + The mass of the carrier accounts for 4%-12% of the mass of the carrier; The specific surface area of ​​the carrier is 80 m 2 / g-1000m 2 / g, pore size is 0.4nm-18nm.

2. The supported Cu as claimed in claim 1 + A bactericidal material, characterized in that The Cu + The particle size of the compound is 1nm-20nm; Preferably, the Cu + Compounds include Cu3P; Preferably, the carrier comprises any one or a combination of at least two of Al2O3, SiO2, ZrO2 or molecular sieve; Preferably, the molecular sieve includes any one of MCM-41 molecular sieve, SBA-5 molecular sieve, X-type molecular sieve, Y-type molecular sieve, ZSM-5 molecular sieve or Beta molecular sieve, or a combination of at least two thereof.

3. A supported Cu as claimed in claim 1 or 2 + The method for preparing a bactericidal material is characterized in that: The preparation method comprises: The copper salt is dissolved in the dispersion of the carrier, dried, and calcined to obtain the Cu-loaded precursor; the Cu-loaded precursor is subjected to reduction heat treatment to prepare the loaded Cu + Sterilization materials; The mass of Cu in the copper salt is 4%-12% of the mass of the carrier.

4. The preparation method according to claim 3, characterized in that: The reduction heat treatment comprises placing a reducing agent and the Cu-loaded precursor in an inert atmosphere, and calcining the reduced agent to prepare the loaded Cu + Sterilization materials; Preferably, the reducing agent comprises hypophosphite; Preferably, the hypophosphite comprises any one of sodium hypophosphite, potassium hypophosphite or calcium hypophosphite or a combination of at least two thereof; Preferably, the copper salt includes any one of copper sulfate, copper chloride, copper nitrate or copper acetate, or a combination of at least two thereof.

5. The preparation method according to claim 4, characterized in that: The reduction heat treatment process further includes uniformly mixing the Cu-loaded precursor and the reducing component before placing the Cu-loaded precursor and the hypophosphite in an inert atmosphere; Preferably, the molar ratio of P in the hypophosphite to Cu in the Cu-loaded precursor is (2-10):

1.

6. The preparation method according to claim 4, characterized in that: The reduction heat treatment process also includes placing the hypophosphite at the upstream end of the inert gas introduction direction and placing the Cu-loaded precursor at the downstream end of the inert gas introduction direction.

7. The preparation method according to claim 3, characterized in that: During the reduction heat treatment process, the temperature of the reduction heat treatment is 250°C-450°C; Preferably, during the reduction heat treatment process, the reduction heat treatment time is 1h-5h; Preferably, the inert gas in the inert atmosphere includes nitrogen and / or noble gas; Preferably, the inert gas comprises argon and / or helium.

8. The preparation method according to claim 3, characterized in that: The drying temperature is 60°C-120°C.

9. The preparation method according to claim 3, characterized in that: The calcination temperature is 400°C-600°C; Preferably, the calcination time is 2h-6h.

10. A supported Cu as claimed in claim 1 + The application of the bactericidal material is characterized in that: The supported Cu + Sterilization materials are used in the field of sterilization of pathogenic microorganisms.

Images