CN117358221A - Activated carbon-based formaldehyde scavenger - Google Patents
Activated carbon-based formaldehyde scavenger Download PDFInfo
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- CN117358221A CN117358221A CN202311275215.XA CN202311275215A CN117358221A CN 117358221 A CN117358221 A CN 117358221A CN 202311275215 A CN202311275215 A CN 202311275215A CN 117358221 A CN117358221 A CN 117358221A
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- activated carbon
- luminescent material
- titanium dioxide
- conversion luminescent
- formaldehyde scavenger
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 397
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 242
- 239000002516 radical scavenger Substances 0.000 title claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 194
- 239000000463 material Substances 0.000 claims abstract description 140
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- -1 rare earth fluoride Chemical class 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 6
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- LSMQKPQSDSZFEZ-UHFFFAOYSA-N C=O.[C] Chemical class C=O.[C] LSMQKPQSDSZFEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
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- 150000004645 aluminates Chemical class 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- 235000019789 appetite Nutrition 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention discloses an active carbon-based formaldehyde scavenger, and belongs to the field of air purification. The active carbon-based formaldehyde scavenger contains active carbon, titanium dioxide and up-conversion luminescent material. The titanium dioxide has the advantages of biochemical inertia, innocuity, good stability and environmental protection, formaldehyde can be catalyzed and decomposed into carbon dioxide and water under the irradiation of ultraviolet light, the ultraviolet light can be converted by the up-conversion luminescent material to absorb visible light, the formaldehyde adsorbed by the activated carbon can be efficiently and rapidly catalyzed and decomposed into carbon dioxide and water under the ultraviolet light condition provided by the up-conversion luminescent material, and the formaldehyde is prevented from being reversely released after the activated carbon is physically adsorbed and saturated, so that secondary pollution is carried out on the environment.
Description
Technical Field
The invention relates to the field of air purification, in particular to an active carbon-based formaldehyde scavenger.
Background
Formaldehyde is colorless and has a pungent odor gas, and has a stimulating effect on eyes, nose, respiratory tract and the like of people. Furniture, building materials and textiles which are often contacted in daily life of human beings release free formaldehyde and are in a long-term stateThe formaldehyde with low concentration can cause people to have poor appetite, weakness and headache, insomnia and the like. When the formaldehyde concentration reaches (11-50) x 10 -6 Acute poisoning and even cancer can occur in humans. In recent years, the problem of scavenging formaldehyde indoors has been the focus of attention both at home and abroad.
The activated carbon has the advantages of high removal efficiency, wide material source range, simple and flexible operation, low cost and the like, and is one of the most effective methods for removing indoor formaldehyde at present. However, the active carbon has limited pores, and the problem of secondary pollution caused by saturated adsorption of formaldehyde in physical adsorption is solved, and the low-concentration formaldehyde is not good in removal efficiency and is easily influenced by environmental temperature and humidity, so that the application space of the active carbon for removing formaldehyde is greatly restricted.
Therefore, there is a need for an improvement in activated carbon that requires the treatment and removal of formaldehyde when physical adsorption is saturated and formaldehyde release is reversed.
Disclosure of Invention
The invention mainly aims to provide an active carbon-based formaldehyde scavenger, which solves the technical problems that the secondary pollution is easily caused by adsorption saturation when active carbon is used for removing formaldehyde, and the purpose of removing formaldehyde is difficult to really achieve.
In order to achieve the above object, the present invention provides an activated carbon-based formaldehyde scavenger, which is characterized in that the activated carbon-based formaldehyde scavenger comprises the following components:
activated carbon, titanium dioxide and an up-conversion luminescent material,
the up-conversion luminescent material comprises an activator, a sensitizer and a matrix material.
In some embodiments of the present application, the activator comprises Er 3+ 、Ho 3+ 、Tm 3+ At least one of (a) and (b);
and/or the sensitizer comprises Yb 3+ ；
And/or the matrix material comprises at least one of rare earth fluoride, rare earth oxide, rare earth halide, and rare earth sulfur-containing compound.
In some embodiments of the present application, the activated carbon has a porosity of 50% or more;
and/or the aperture range of the activated carbon is 50nm-100 nm.
And/or the particle size of the activated carbon ranges from 0.2 to 0.6mm.
In some embodiments of the present application, the titania and the up-conversion luminescent material are combined to obtain a titania doped up-conversion luminescent material.
In some embodiments of the present application, the titania-doped up-conversion luminescent material is NaYF 4 :Pr 3+ ，Li + @TiO 2 ；
And/or the titanium dioxide doped up-conversion luminescent material comprises a powder type titanium dioxide doped up-conversion luminescent material or a water-based titanium dioxide doped up-conversion luminescent material.
In some embodiments of the present application, the titania-doped up-conversion luminescent material is coated on the surface of the activated carbon;
and/or the active carbon-based formaldehyde scavenger further comprises a load, and the titanium dioxide doped up-conversion luminescent material is coated on the surface of the load.
In some embodiments of the present application, the support comprises activated carbon or a package for packaging the activated carbon-based formaldehyde scavenger.
In some embodiments of the present application, the activated carbon-based formaldehyde scavenger comprises an outer package that is light permeable.
In some embodiments of the present application, the activated carbon-based formaldehyde scavenger comprises a light-accumulating self-luminescent material.
In some embodiments of the present application, the light-accumulating self-luminous material may be coated on an inner wall surface of the outer package to form a light-accumulating coating.
The invention has the beneficial effects that:
the active carbon-based formaldehyde scavenger contains active carbon, titanium dioxide and an up-conversion luminescent material, the titanium dioxide has the advantages of biochemical inertia, no toxicity and harm, good stability and environmental protection, formaldehyde can be catalyzed and decomposed into carbon dioxide and water under the irradiation of ultraviolet light, the ultraviolet light can be converted by the up-conversion luminescent material to absorb visible light, the titanium dioxide can efficiently and rapidly catalyze and decompose formaldehyde absorbed by the active carbon into carbon dioxide and water under the ultraviolet light condition provided by the up-conversion luminescent material, and the formaldehyde is reversely released after the physical absorption of the active carbon is prevented from secondary pollution to the environment.
The application can also utilize the light-storage self-luminous material to absorb natural light through adding the light-storage self-luminous material, so that the active carbon-based formaldehyde scavenger can provide a light source through the light-storage self-luminous material to emit light even at night without natural light or in dim corners, the up-conversion luminescent material converts light emitted by the light-storage self-luminous material into ultraviolet light, and the titanium dioxide degrades formaldehyde by utilizing the ultraviolet light. Therefore, the formaldehyde absorbing and degrading device can absorb and degrade formaldehyde even at night or dim corners without natural light, and has strong practicability.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The description as it relates to "first", "second", etc. in the present invention is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The activated carbon has the advantages of high removal efficiency, wide material source range, simple and flexible operation, low cost and the like, and is one of the most effective methods for removing indoor formaldehyde at present. However, the active carbon has limited pores, and the problem of secondary pollution caused by saturated adsorption of formaldehyde in physical adsorption is solved, and the low-concentration formaldehyde is not good in removal efficiency and is easily influenced by environmental temperature and humidity, so that the application space of the active carbon for removing formaldehyde is greatly restricted.
In view of this, the present invention provides an activated carbon-based formaldehyde scavenger comprising the following components:
activated carbon, titanium dioxide and an up-conversion luminescent material,
the up-conversion luminescent material comprises an activator, a sensitizer and a matrix material.
In some embodiments, the activator comprises Er 3+ 、Ho 3+ 、Tm 3+ At least one of them.
In some embodiments, the sensitizer comprises Yb 3+ 。
In some embodiments, the host material includes at least one of a rare earth fluoride, a rare earth oxide, a rare earth halide, and a rare earth sulfur-containing compound.
The activated carbon has an adsorption effect on formaldehyde, and can adsorb and aggregate formaldehyde in the air.
The titanium dioxide has the advantages of biochemical inertia, innocuity, good stability and environmental protection, and can catalytically decompose formaldehyde into carbon dioxide and water under the irradiation of ultraviolet light.
When the up-conversion material absorbs excitation light, the matrix material provides reaction sites, the sensitizer absorbs the energy of the excitation light and then transmits the excitation light to the activator, photons which absorb the energy in the activator transition from a ground state to the excitation state and then return to the ground state, and meanwhile, the photons are released to generate up-conversion luminescence.
The active carbon-based formaldehyde scavenger comprises the active carbon, titanium dioxide and the up-conversion luminescent material, wherein the up-conversion luminescent material can absorb visible light and convert the visible light into ultraviolet light, and the titanium dioxide can quickly and efficiently catalyze and decompose formaldehyde absorbed by the active carbon into carbon dioxide and water under the ultraviolet light condition provided by the up-conversion luminescent material, so that the active carbon is prevented from being saturated by physical absorption and then reversely releasing formaldehyde, and secondary pollution is carried out on the environment.
In some embodiments, the porosity of the activated carbon is above 50%, e.g., may be above 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, etc., values less than 100%. The activated carbon has larger porosity and is beneficial to improving the adsorption effect on formaldehyde, so that the contact between titanium dioxide and formaldehyde is enhanced, and the titanium dioxide can quickly and efficiently catalyze and decompose the formaldehyde into carbon dioxide and water.
In some embodiments, the pore size of the activated carbon is in the range of 50nm-100nm, and may be any one of the pore size values in the range of 50nm-100nm, such as 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc. The aperture of the activated carbon is in the range of 50nm-100nm, the aperture is larger, and the adsorption effect on formaldehyde is improved, so that the contact between titanium dioxide and formaldehyde is enhanced, and the titanium dioxide can quickly and efficiently catalyze and decompose the formaldehyde into carbon dioxide and water.
In some embodiments, the activated carbon has a particle size in the range of 0.2-0.6 mm, has a large specific surface area, and can adsorb more formaldehyde.
In some embodiments, the titanium dioxide and the up-conversion luminescent material may also be combined to provide a composite titanium dioxide doped up-conversion luminescent material.
It is understood that the titania-doped up-conversion luminescent material of the present invention is a composite material obtained by combining titania and up-conversion luminescent material by physical or chemical methods, and may be prepared in a manner well known to those skilled in the art. The up-conversion luminescent material is combined with the titanium dioxide component to form a composite material, the up-conversion luminescent material and the titanium dioxide can be firmly combined together, the titanium dioxide can be uniformly distributed on the up-conversion luminescent material, more catalytic active sites of the titanium dioxide are exposed, the receiving area of the titanium dioxide for ultraviolet light is increased, after the up-conversion luminescent material absorbs visible light and converts the visible light into ultraviolet light, the ultraviolet light can be rapidly utilized by the titanium dioxide, formaldehyde is catalytically degraded into carbon dioxide and water, and the purpose of rapid and efficient catalytic degradation of formaldehyde is achieved.
The invention does not limit the mode of doping the up-conversion luminescent material with titanium dioxide, and can combine the up-conversion luminescent material with titanium dioxide by a chemical method or a physical method to form the composite material titanium dioxide doped up-conversion luminescent material.
In some embodiments, the titania and the upconverting luminescent material may be combined with the titania to form a titania doped upconverting luminescent material by a sol gel process, a solution chemistry process, a hydrothermal process, a physical vapor deposition process, or a co-precipitation process.
Illustratively, the titanium dioxide and the up-conversion luminescent material are combined with the titanium dioxide by a sol-gel process to form a composite. The above-mentioned conversion luminescent material NaYF 4 :Pr 3+ ,Li + For example, the up-conversion luminescent material NaYF 4 :Pr 3+ ,Li + Dissolving and dispersing into absolute ethyl alcohol, and then adding butyl titanate, stirring and mixing to obtain a precursor A; mixing water and absolute ethyl alcohol to obtain a precursor B. Dropwise adding the precursor B into the precursor A under the condition of stirring, continuously stirring and then drying to obtain a solid material, calcining and cooling the solid material to obtain the composite material titanium dioxide doped up-conversion luminescent material NaYF 4 :Pr 3+ ,Li + @TiO 2 。
In some embodiments, the luminescent material NaYF may be up-converted by ultrasound 4 :Pr 3+ ,Li + Dissolving and dispersing into absolute ethyl alcohol, which is beneficial to accelerating the dispersion of up-conversion luminescent materials.
In some embodiments, precursor B is added dropwise to precursor a at a drop rate of 1 ml/min.
In some embodiments, precursor B is added dropwise to precursor A, and the solid material is obtained by continuously stirring for 1-12 h and then drying at 50-70 ℃.
In some embodiments, the solid material is calcined at 400-500 ℃.
In some embodiments, the calcination time of the solid material is 1 to 3 hours.
In some embodiments, the rate of temperature rise of the calcination is 2 ℃/min.
In some embodiments, cooling to room temperature yields a composite titania doped up-conversion luminescent material NaYF 4 :Pr 3+ ,Li + @TiO 2 。
According to the up-conversion luminescent material obtained by the sol-gel method, a heterostructure is formed between the titanium dioxide and the up-conversion luminescent material, the titanium dioxide and the up-conversion luminescent material can be firmly combined together, the titanium dioxide can be uniformly distributed on the up-conversion luminescent material, more catalytic active sites are exposed, the receiving area of the up-conversion luminescent material for ultraviolet light is increased, and after the up-conversion luminescent material absorbs visible light to convert the visible light into the ultraviolet light, the titanium dioxide can rapidly utilize the ultraviolet light to catalytically degrade formaldehyde into carbon dioxide and water.
In some embodiments, the titania-doped up-conversion luminescent material is NaYF 4 :Pr 3+ ，Li + @TiO 2 。NaYF 4 Is currently considered to be the most efficient host material for luminescence, up-conversion material NYF 4 Essentially by doping the matrix with sensitizer Li + Absorbing visible light and passing through doped luminous center Pr 3+ The visible light is converted into ultraviolet light in UVC wave band, and the titanium dioxide utilizes the ultraviolet light to achieve the purpose of catalyzing and degrading formaldehyde.
The invention is not limited to the dosage form of the titanium dioxide doped up-conversion luminescent material, and can be powder type titanium dioxide doped up-conversion luminescent material or water type titanium dioxide doped up-conversion luminescent material.
The aqueous titanium dioxide doped up-conversion luminescent material can be obtained by dissolving a powder titanium dioxide doped up-conversion luminescent material into a solvent, wherein the solvent comprises water. In one embodiment, a film forming agent can be added into water, which is favorable for forming a film layer with stronger binding force on the substrate by the water-based titanium dioxide doped up-conversion luminescent material.
In some embodiments, the weight ratio of the powdered titanium dioxide doped up-conversion luminescent material to water is (0.5-3): 100, under the condition of the weight ratio, the powder type titanium dioxide doped up-conversion luminescent material can be uniformly dispersed in water to form the water aqua type titanium dioxide doped up-conversion luminescent material.
In some embodiments, the weight ratio of the water to the powder-type titanium dioxide doped up-conversion luminescent material to the film forming agent is 100: (0.5-3): (1-10). Under the condition of the weight ratio, the powder type titanium dioxide doped up-conversion luminescent material can be uniformly dispersed in water to form the water aqua type titanium dioxide doped up-conversion luminescent material, and has a good film forming effect.
In some embodiments, when the titania-doped up-conversion luminescent material is a powdered titania-doped up-conversion luminescent material, the powdered titania-doped up-conversion luminescent material may be mixed with activated carbon to form an activated carbon-based formaldehyde scavenger.
In some embodiments, when the titanium dioxide doped up-conversion luminescent material is an aqueous titanium dioxide doped up-conversion luminescent material, the aqueous titanium dioxide doped up-conversion luminescent material can be coated on the surface of the active carbon to form a film layer, which is favorable for fully exposing active sites of titanium dioxide, increasing the receiving area of ultraviolet light, and simultaneously increasing the contact area of the up-conversion luminescent material and visible light, accelerating the generation of ultraviolet light, thereby realizing the purpose of high-efficiency and rapid catalytic degradation of formaldehyde.
In some embodiments, the activated carbon-based formaldehyde scavenger further comprises a support, and the titania-doped up-conversion luminescent material may be coated on the surface of the support, and then the support and the activated carbon are uniformly mixed.
The present invention is not limited to the kind of the above-mentioned carriers, and includes activated carbon or a package for packaging the activated carbon-based formaldehyde scavenger. When the load is a package for packaging the activated carbon-based formaldehyde scavenger, the titanium dioxide doped up-conversion luminescent material is coated on the inner wall of the package, so that the load and the activated carbon are positioned in the same space, and formaldehyde absorbed by the activated carbon can be decomposed in time.
When the load is activated carbon, the activated carbon can be soaked in the aqueous titanium dioxide doped up-conversion luminescent material, and a titanium dioxide doped up-conversion luminescent material film layer is formed on the surface of the activated carbon, so that the catalytic active site of the titanium dioxide is fully exposed, the receiving area of the titanium dioxide for ultraviolet light is increased, and the rapid and efficient formaldehyde removal effect is realized. And the active carbon is used as a load, so that the ratio of the active carbon to the titanium dioxide doped up-conversion luminescent material in the active carbon-based formaldehyde scavenger can be increased, and the economic benefit is improved.
When the load is a package, the package comprises a soft package or a hard package, the package is made of a light-permeable material, and the water-type titanium dioxide doped up-conversion luminescent material can be coated on the inner wall of the package, so that the load and the activated carbon are positioned in the same space, and formaldehyde absorbed by the activated carbon can be decomposed in time; in addition, a layer of adhesive can be coated on the inner wall surface of the package, and then the powder-type titanium dioxide doped up-conversion luminescent material is coated, so that the fixation of the powder-type titanium dioxide doped up-conversion luminescent material is facilitated.
In some embodiments, the activated carbon-based formaldehyde scavenger further comprises an outer package, and other materials such as activated carbon, titanium dioxide doped up-conversion luminescent materials and the like are placed inside the outer package, so that the activated carbon-based formaldehyde scavenger is placed at each corner of a room, which can be contacted with visible light, and the purpose of comprehensively and rapidly catalyzing and degrading formaldehyde in the room is achieved.
The overwrap of the present invention includes a flexible package or a rigid package such as a carton, a plastic box, a cloth bag, and the like.
When the outer package is a flexible package, activated carbon, titanium dioxide and up-conversion luminescent materials can be used; or activated carbon and titanium dioxide doped up-conversion luminescent material; or active carbon with the surface coated with titanium dioxide doped up-conversion luminescent material; or the active carbon and the load coated with the titanium dioxide doped up-conversion luminescent material are placed in a flexible package to form the active carbon-based formaldehyde cleaning agent. The soft package active carbon-based formaldehyde cleaner is arranged at each corner of the room, so that the formaldehyde in the room can be comprehensively and rapidly catalyzed and degraded.
When the outer package is a hard package, activated carbon, titanium dioxide and up-conversion luminescent materials can be used for preparing the light-emitting material; or activated carbon and titanium dioxide doped up-conversion luminescent material; or active carbon with the surface coated with titanium dioxide doped up-conversion luminescent material; or the active carbon and the load coated with the titanium dioxide doped up-conversion luminescent material are placed in a hard package to form the boxed active carbon-based formaldehyde cleaning agent. The hard-packed active carbon-based formaldehyde cleaner is arranged at each corner of the room, so that the formaldehyde in the room can be comprehensively and rapidly catalyzed and degraded.
In some embodiments, the outer package is light-permeable, and the invention is not limited to the light-permeable manner of the outer package, and the outer package can be made of light-permeable materials, or light holes and the like can be designed on the outer package. The light-permeable outer package can provide a light source, the up-conversion luminescent material converts the light source into ultraviolet light, and the titanium dioxide can efficiently and rapidly catalytically decompose formaldehyde absorbed by the activated carbon into carbon dioxide and water under the ultraviolet light condition, so that the activated carbon is prevented from being physically adsorbed and saturated to reversely release formaldehyde, and secondary pollution is caused to the environment.
In some embodiments, the titanium dioxide doped up-conversion luminescent material may be coated on the interior wall of the overpack, and then activated carbon placed inside the overpack.
In some embodiments, the activated carbon-based formaldehyde scavenger comprises a light-storage self-luminous material, the light-storage self-luminous material has the functions of absorbing light, accumulating light and emitting light, after absorbing visible light for 10-20 minutes, the light-emitting effect of more than 10 hours can be continuously maintained in a dark place, the up-conversion luminescent material converts a light source emitted by the light-storage self-luminous paint into ultraviolet light, and under the ultraviolet light condition provided by the up-conversion luminescent material, the titanium dioxide can efficiently and rapidly catalytically decompose formaldehyde absorbed by the activated carbon into carbon dioxide and water, so that the formaldehyde is reversely released after the activated carbon is physically absorbed fully, and secondary pollution is caused to the environment. Therefore, the active carbon-based formaldehyde scavenger can absorb and degrade formaldehyde even at night or in dim corners without natural light, and has strong practicability.
In some embodiments, a light-accumulating self-luminescent material may be coated on the interior wall surface of the outer package to form a light-accumulating self-luminescent coating.
In some embodiments, a light-accumulating self-luminescent material may also be coated on the support to form a light-accumulating self-luminescent coating.
In some embodiments, the light-accumulating self-luminescent material includes an aluminate-system light-accumulating self-luminescent material, a silicate-system light-accumulating self-luminescent material, and a sulfide-system light-accumulating self-luminescent material.
In some embodiments, the sulfide-based light-accumulating self-luminescent material includes at least one of zinc sulfide, zinc sulfide pot, silver sulfide, barium sulfide, calcium sulfide, for example, including at least one of ZnS: cu series, caS: bi series, or CaS: eu series.
In some embodiments, the aluminate system light-accumulating self-luminescent material comprises CaAl 2 O 4 :Eu，Nb、Sr 4 Al l4 O 25 :Eu，Dy、SrAl 2 O 4 At least one of Eu and Dy.
It should be noted that the above examples are only some examples of the activated carbon-based formaldehyde scavenger of the present invention, and are not to be construed as limiting the present invention.
The technical scheme of the present invention will be further described in detail with reference to the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
The activated carbon-based formaldehyde scavenger is prepared by the following preparation method:
step one: preparing materials:
titanium dioxide;
up-conversion luminescent material: naYF 4 :Pr 3+ ，Li + ；
Activated carbon: the porosity is more than 50%, the pore diameter ranges from 50nm to 100nm, and the particle size ranges from 0.2 mm to 0.6mm.
Step two: preparation of activated carbon-based formaldehyde scavenger
And uniformly mixing the titanium dioxide, the up-conversion luminescent material and the activated carbon to obtain the activated carbon-based formaldehyde scavenger.
Example 2
The activated carbon-based formaldehyde scavenger is prepared by the following preparation method:
step one: preparation of materials
Titanium dioxide and NaYF by sol-gel method 4 :Pr 3+ ，Li + Compounding to obtain powdered titania doped up-conversion luminescent material NaYF 4 :Pr 3+ ，Li + @TiO 2 ；
Activated carbon: the porosity is more than 50%, the pore diameter ranges from 50nm to 100nm, and the particle size ranges from 0.2 mm to 0.6mm.
Step two: preparation of activated carbon-based formaldehyde scavenger
And mixing the titanium dioxide doped up-conversion luminescent material and the activated carbon uniformly to obtain the activated carbon-based formaldehyde scavenger.
Example 3
Step one: preparation of materials
100 parts by weight of water and 0.5 part by weight of NaYF prepared in example 2 4 :Pr 3+ ，Li + @TiO 2 Mixing, mechanically stirring, and making into water-feeding agent type NaYF 4 :Pr 3+ ，Li + @TiO 2 ；
Activated carbon: the porosity is more than 50%, the pore diameter is 50nm-100nm, and the particle diameter is 0.2-0.6 mm.
Step two: preparation of activated carbon-based formaldehyde scavenger
The acrylic paint is sprayed on the inner wall and the bottom of a 200mL transparent glass container, and then the inner wall and the bottom of the transparent glass container are coated with the water-based NaYF 4 :Pr 3+ ，Li + @TiO 2 Formation of NaYF 4 :Pr 3+ ，Li + @TiO 2 Film, then in transparent glass containerAdding 50g of active carbon, and incompletely covering NaYF 4 :Pr 3+ ，Li + @TiO 2 And (3) the film is used for obtaining the active carbon-based formaldehyde scavenger taking the transparent glass container as an outer package.
Example 4
Step one: preparation of materials
With 100 parts by weight of water and 1.5 parts by weight of NaYF prepared in example 2 4 :Pr 3+ ，Li + @TiO 2 Mixing, mechanically stirring, and making into water-feeding agent type NaYF 4 :Pr 3+ ，Li + @TiO 2 ；
Activated carbon: the porosity is more than 50%, the pore diameter ranges from 50nm to 100nm, and the particle size ranges from 0.2 mm to 0.6mm.
Step two: preparation of activated carbon-based formaldehyde scavenger
The acrylic paint is sprayed on the inner wall and the bottom of a 200mL transparent glass container, and then the inner wall and the bottom of the transparent glass container are coated with the water-based NaYF 4 :Pr 3+ ，Li + @TiO 2 Formation of NaYF 4 :Pr 3+ ，Li + @TiO 2 Film, then put 50g of active carbon in a transparent glass container, the active carbon is not completely covered with NaYF 4 :Pr 3+ ，Li + @TiO 2 And (3) the film is used for obtaining the active carbon-based formaldehyde scavenger taking the transparent glass container as an outer package.
Example 5
Step one: preparation of materials
100 parts by weight of water and 3 parts by weight of NaYF prepared in example 2 4 :Pr 3+ ，Li + @TiO 2 Mixing, mechanically stirring, and making into water-feeding agent type NaYF 4 :Pr 3+ ，Li + @TiO 2 ；
Activated carbon: the porosity is more than 50%, the pore diameter ranges from 50nm to 100nm, and the particle size ranges from 0.2 mm to 0.6mm.
Step two: preparation of activated carbon-based formaldehyde scavenger
The acrylic paint was sprayed on the inner wall and bottom of a 200mL transparent glass container, and then on the inner wall and bottom of the transparent glass containerWater-coating agent type NaYF 4 :Pr 3+ ，Li + @TiO 2 Formation of NaYF 4 :Pr 3+ ，Li + @TiO 2 Film, then put 50g of active carbon in a transparent glass container, the active carbon is not completely covered with NaYF 4 :Pr 3+ ，Li + @TiO 2 And (3) the film is used for obtaining the active carbon-based formaldehyde scavenger packaged by a transparent glass container.
Performance test 1:
5 identical light-transmitting patterns 1m were prepared 3 Placing in a place capable of receiving visible light, placing 1mL of formaldehyde solution in the sealed test box, naturally volatilizing for 12h to form formaldehyde gas with a certain concentration, taking out the non-evaporated formaldehyde solution, and measuring the initial concentration C of formaldehyde in the sealed test box 0 。
50g of the activated carbon-based formaldehyde scavenger of example 1 and 50g of the activated carbon-based formaldehyde scavenger of example 2 were placed in 2 different 200mL transparent glass containers, and the 2 transparent glass containers were placed in 2 different closed test chambers, respectively, and the formaldehyde concentration C in the closed test chambers at different times was measured 1 The formaldehyde removal rate in the closed test box at different times was calculated.
Meanwhile, the transparent glass containers of examples 3 to 5 filled with the activated carbon-based formaldehyde scavenger were directly placed in the remaining 3 closed test boxes, respectively, and the formaldehyde concentration C in the closed test boxes at different times was measured 1 The formaldehyde removal rate in the closed test box at different times was calculated.
Formaldehyde removal (%) = (C) 0 －C 1 )/C 0
The test results are shown in Table 1.
TABLE 1 examples 1-5 Formaldehyde removal rates (%)
| Time | 1h | 2h | 3h | 4h | 5h | 6h | 5Day | 10Day |
| Example 1 | 75 | 79 | 82 | 83 | 86 | 90 | 93 | 98 |
| Example 2 | 72 | 75 | 79 | 80 | 80 | 80 | 91 | 94 |
| Example 3 | 83 | 86 | 90 | 90 | 90 | 90 | 99 | 99 |
| Example 4 | 89 | 92 | 94 | 94 | 94 | 94 | 99 | 99 |
| Example 5 | 81 | 82 | 85 | 90 | 93 | 95 | 99 | 99 |
Performance test 2:
prepare 2 identical opaque 1m 3 1mL of formaldehyde solution is put into the closed test box, formaldehyde gas with certain concentration is formed by natural volatilization for 12h, then the unvaporized formaldehyde solution is taken out, and the initial concentration C of formaldehyde in the closed test box is measured 0 。
2 pieces of 200mL transparent glass containers were coated with a light-accumulating self-luminous material ZnS: cu on the inner wall surface of each glass container, and 50g of the glass container of example 1 was then put into contact with the glass containerThe carbon-based formaldehyde scavenger and 50g of the activated carbon-based formaldehyde scavenger of example 2 were placed in the above 2 transparent glass containers, respectively. The 2 transparent glass containers are firstly placed in a light environment to absorb visible light for 10 to 20 minutes, and then are respectively placed in the 2 opaque 1m 3 In the closed test box, the formaldehyde concentration C in the light-proof closed test box at different times is measured 1 And calculating the formaldehyde removal rate in the light-tight closed test box at different times.
Formaldehyde removal (%) = (C) 0 -C 1 )/C 0
The test results are shown in Table 2.
TABLE 2 Formaldehyde removal Rate (%)
| Time | 1h | 3h | 5h | 8h | 10h |
| Example 1 | 76 | 81 | 85 | 89 | 90 |
| Example 2 | 82 | 89 | 90 | 91 | 92 |
As can be seen from Table 1, the activated carbon-based formaldehyde scavenger of the embodiment of the invention can efficiently and rapidly catalyze and decompose formaldehyde absorbed by activated carbon into carbon dioxide and water, and prevent the activated carbon from releasing formaldehyde reversely after physical adsorption saturation, thereby secondary pollution to the environment is caused.
As can be seen from Table 2, the activated carbon formaldehyde scavenger of the embodiment of the invention is filled into a package coated with a light-storage type self-luminous material, and is firstly absorbed for 10-20 min, the up-conversion luminescent material in the activated carbon formaldehyde scavenger can convert self-luminescence emitted by the light-storage type self-luminous material into ultraviolet light, and the titanium dioxide can efficiently and rapidly catalyze and decompose formaldehyde absorbed by the activated carbon into carbon dioxide and water under the condition of ultraviolet light, so that the activated carbon is prevented from being absorbed fully by physics and then reversely releasing formaldehyde, and secondary pollution is caused to the environment. Therefore, the active carbon-based formaldehyde scavenger can absorb and degrade formaldehyde even at night or in dim corners without natural light, and has strong practicability.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.
Claims (10)
1. An activated carbon-based formaldehyde scavenger, characterized in that the activated carbon-based formaldehyde scavenger comprises the following components:
activated carbon, titanium dioxide and an up-conversion luminescent material,
the up-conversion luminescent material comprises an activator, a sensitizer and a matrix material.
2. According to claim 1The activated carbon-based formaldehyde scavenger is characterized in that the activator comprises Er 3+ 、Ho 3+ 、Tm 3+ At least one of (a) and (b);
and/or the sensitizer comprises Yb 3+ ；
And/or the matrix material comprises at least one of rare earth fluoride, rare earth oxide, rare earth halide, and rare earth sulfur-containing compound.
3. The activated carbon-based formaldehyde scavenger according to claim 1, wherein the activated carbon has a porosity of 50% or more;
and/or the aperture range of the activated carbon is 50nm-100 nm;
and/or the particle size of the activated carbon ranges from 0.2 to 0.6mm.
4. The activated carbon-based formaldehyde scavenger according to claim 1, wherein the titanium dioxide and the up-conversion luminescent material are combined to obtain a titanium dioxide doped up-conversion luminescent material.
5. The activated carbon-based formaldehyde scavenger according to claim 4, characterized in that the titania doped up-conversion luminescent material is NaYF 4 :Pr 3+ ，Li + @TiO 2 ；
And/or the titanium dioxide doped up-conversion luminescent material comprises a powder type titanium dioxide doped up-conversion luminescent material or a water-based titanium dioxide doped up-conversion luminescent material.
6. The activated carbon-based formaldehyde cleaner according to claim 4, wherein the titanium dioxide doped up-conversion luminescent material is coated on the surface of the activated carbon;
and/or the active carbon-based formaldehyde scavenger further comprises a load, and the titanium dioxide doped up-conversion luminescent material is coated on the surface of the load.
7. The activated carbon-based formaldehyde scavenger according to claim 6, wherein the support comprises activated carbon or a package for packaging the activated carbon-based formaldehyde scavenger.
8. The activated carbon-based formaldehyde scavenger according to any one of claims 1 to 7, wherein the activated carbon-based formaldehyde scavenger comprises an overwrap, the overwrap being light permeable.
9. The activated carbon-based formaldehyde scavenger according to claim 8, wherein the activated carbon-based formaldehyde scavenger comprises a light-accumulating self-luminescent material.
10. The activated carbon-based formaldehyde scavenger according to claim 9, wherein the light-accumulating self-luminescent material is coatable on an inner wall surface of the outer package with a light-accumulating coating.
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