CN105344345B - A kind of optic catalytic composite material with conditioning performance and preparation method thereof - Google Patents
A kind of optic catalytic composite material with conditioning performance and preparation method thereof Download PDFInfo
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- CN105344345B CN105344345B CN201510692779.2A CN201510692779A CN105344345B CN 105344345 B CN105344345 B CN 105344345B CN 201510692779 A CN201510692779 A CN 201510692779A CN 105344345 B CN105344345 B CN 105344345B
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- palmitic acid
- tio
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- palmityl alcohol
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 35
- 230000003750 conditioning effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 74
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 55
- 239000012782 phase change material Substances 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims abstract description 36
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 235000021314 Palmitic acid Nutrition 0.000 claims abstract description 18
- 229960000541 cetyl alcohol Drugs 0.000 claims abstract description 18
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940070765 laurate Drugs 0.000 claims description 47
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- -1 Palmityl Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 36
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- ZNHBVQBSJKAINO-UHFFFAOYSA-N dodecanoic acid;hexadecanoic acid Chemical compound CCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCC(O)=O ZNHBVQBSJKAINO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 229940098695 palmitic acid Drugs 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 241001122767 Theaceae Species 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- B01D2258/00—Sources of waste gases
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention discloses a kind of optic catalytic composite material with conditioning performance and preparation method thereof, belong to functional material and energy-saving building technology field.The composite includes phase-change material, catalysis material etc., and the phase-change material is palmityl alcohol, palmitic acid and lauric mixture；The catalysis material is Eu Ce/TiO2.The preparation of light catalyzed coating of the present invention includes 3 steps：(1) preparation of palmityl alcohol palmitic acid laurate phase-change material, (2) Eu Ce/TiO2The preparation of catalysis material, (3) have the preparation of the optic catalytic composite material of conditioning performance.Optic catalytic composite material of the present invention with conditioning performance can be in Photo-Catalytic Degradation of Formaldehyde under visible light source and regulation indoor temperature and humidity, it is effectively improved indoor environment comfort level and has changed kind indoor air quality, building energy consumption is reduced, meets the development trend of national green ecological architectural material.
Description
Technical field
The invention belongs to functional material and energy-saving building technology field, and in particular to a kind of light with conditioning performance
Catalytic composite materials and preparation method thereof.
Background technology
Indoor environment is as the space of the time of life 80% activity, and its comfort level is most important, for a long time in order to meet
Requirement of the people to indoor environment comfort level, employs a large amount of ornament materials and a variety of active modes, such as：Wood-based plate is built graceful
The interior space, heating and refrigeration plant regulation indoor temperature, humidifier control indoor humidity etc..But rely on manually heat,
Though the equipment such as refrigeration and humidification can provide more comfortable indoor environment, need to consume the substantial amounts of energy, and equipment makes
Need the gravity-flow ventilation condition to indoor environment to limit during, easily cause " indoor comprehensive disease " disease；This external equipment
It is difficult to carry out effective cleaning to its pipeline in runtime, easily causes microbial growth after long-term use, cause indoor environment
The problem of secondary pollution.
At present, the research around Indoor Environment Safety and Its, comfort level and building energy conservation Synergy has deployed and obtained successively
To great attention, wherein building space enclosing structure material (having " passive regulating power ") and N-type semiconductor material (has " low temperature
Deep oxidation ability ") building, material, environment and the interest of security fields are caused, especially excite to new function material
Exploration, with meet people to build living environment requirement.Utilize " the passive regulating power " of material or " low temperature deep oxidation
Ability " and develop the construction material with energy-saving and environmental protection performance have a variety of, being applied to building inner surface can be preferably
Play regulation indoor temperature and humidity, purify the effect of air.To for conscientiously reduction building energy consumption, improve indoor environment comfort level and
The certain technical support of indoor air quality offer and theoretical foundation are provided.
The content of the invention
In order to realize the optic catalytic composite material with conditioning performance, the present invention first with double rare earth metals (Eu,
Ce) to TiO2Modification is doped, Eu-Ce/TiO is formed2, then utilize Eu-Ce/TiO2Three-D space structure and palmityl alcohol-
Palmitic acid-laurate is combined, and is desirably to obtain low production cost, Photo-Catalytic Degradation of Formaldehyde and tune under visible light source
Save the composite of indoor temperature and humidity.
In order to solve the above technical problems, the present invention is achieved by the following technical programs.
The invention provides a kind of optic catalytic composite material with conditioning performance, the composite presses quality percentage
It is as follows than being formulated：
Phase-change material 10.0%~30.0%
Catalysis material 70.0%~90.0%
The phase-change material is palmityl alcohol, palmitic acid and lauric mixture, and its phase transition temperature is 21.0 DEG C~30.0
℃；The catalysis material is Eu-Ce/TiO2, its particle diameter is 180nm~220nm.
Invention also provides a kind of preparation method of the above-mentioned optic catalytic composite material with conditioning performance, bag
Include following steps：
(1) preparation of palmityl alcohol-palmitic acid-laurate phase-change material：By palmityl alcohol, palmitic acid and lauric mixture
It is put into container, after with constant temperature blender with magnetic force under 2000r/min, 65 DEG C of water bath conditions mixture dissolving and 4h being stirred
Obtain palmityl alcohol-palmitic acid-laurate phase-change material.Palmityl alcohol, palm fibre in the palmityl alcohol-palmitic acid-laurate phase-change material
The sour and lauric mass fraction ratio of palmitic acid is 20~40:10~30:40~60；
(2)Eu-Ce/TiO2The preparation of catalysis material：Match, use by butyl titanate and absolute ethyl alcohol volume ratio 2: 5
Constant temperature blender with magnetic force obtains homogeneous transparent solution after stirring 30min under the conditions of 1200r/min, then will be dissolved with europium nitrate and nitre
The dilute hydrochloric acid solution of sour cerium is mixed in being slowly added to above-mentioned solution under 2000r/min stirrings using watery hydrochloric acid or weak aqua ammonia adjustment
The pH value of liquid is 4~8, and lyosol is obtained after 2000r/min stirrings 45min, and ageing forms xerogel indoors, takes out
Dried after filter, washing, then xerogel is put into middle temperature experimental furnace and is raised to 400 DEG C~600 DEG C with 2 DEG C/min, constant temperature 2h, from
Room temperature so is cooled to, Eu-Ce/TiO is obtained2Catalysis material, the Eu-Ce/TiO2Eu-Ce total moles hundred in catalysis material
Fraction is 1%~5%, Eu and Ce mol ratios 3~1：1~3.
(3) preparation of the optic catalytic composite material with conditioning performance：Match somebody with somebody according to the formula described in claim 1
Than the palmityl alcohol-palmitic acid-laurate phase-change material for preparing step (1) is added to the Eu-Ce/TiO of step (2) preparation2Light
Mixture is formed in catalysis material.Vacuum is put into after mixture is stirred into 30min under 2000r/min, 65 DEG C of water bath conditions
Dry and 4h is dried for the standard atmospheric pressure of 0.5 standard atmospheric pressure~0.9, the vacuum drying chamber that temperature is 80 DEG C, then in ring
Natural cooling under border, so circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material fully absorbs palmityl alcohol-palmitic acid-moon
Cinnamic acid phase-change material.Finally Eu-Ce/TiO is washed using absolute ethyl alcohol2Palmityl alcohol-palmitic acid of catalysis material remained on surface-
Laurate phase-change material, obtains the optic catalytic composite material with conditioning performance.
The principles of science of the present invention：
(1) palmityl alcohol-palmitic acid-laurate phase-change material is to need to absorb (or releasing) greatly when undergoing phase transition using material
The property of calorimetric amount stores or released heat energy, and then reaches the purpose of adjustment, control operation source or surrounding materials environment temperature.
The consumption of the building energies such as electric power, natural gas not only can be effectively reduced, lowers indoor environment temperature fluctuation, improves indoor environment
Hot comfort, and can be that practical application of the solar energy of low cost, high cleaning in heating and refrigeration plant creates conditions.
(2)Eu-Ce/TiO2Catalysis material is effectively to suppress TiO using Eu ions and Ce ion dopings2Phase transformation, that is, exist
TiO2Eu ions and Ce ions have certain synergy in system, and this synergy makes Eu-Ce/TiO2Catalysis material
Photocatalytic activity is greatly improved.While Eu ions and Ce ion dopings TiO2Capture light induced electron or cavitation, suppression can be improved
Make the compound of the two to bury in oblivion, so as to improve the response to visible light source.
(3) optic catalytic composite material with conditioning performance is to utilize Eu-Ce/TiO2Catalysis material surface it is big
Micropore is measured, wherein palmityl alcohol-palmitic acid-laurate phase-change material is wrapped in large hole in the presence of surface tension and capillary
In the micropore in footpath, the water utilization physical absorption in air is wet to being inhaled and (being put) in the micropore of smaller aperture due.So as to realize
The perfect unity of temperature adjusting performance, humidity and photocatalysis performance.
(4) palmityl alcohol-palmitic acid-laurate phase-change material and Eu-Ce/TiO2It is compound, on the one hand utilize material interface heat
Wet coupling mechanism, conducts heat when realizing heat transfer when mass transfer, mass transfer, so as to improve the synthesis conditioning performance of product；The opposing party
Face utilizes Eu-Ce/TiO2Photocatalysis formaldehyde gas produces H2O and moisture pick-up properties, can further enhance the humidity of product,
Promote the reaction of photocatalysis formaldehyde gas to be carried out to positive direction, greatly improve photocatalysis effect.
Compared with prior art, the invention has the advantages that：
1st, the present invention utilizes Eu-Ce/TiO2Catalysis material had both played Eu-Ce and has been modified TiO as matrix material2Light
Catalytic performance, has played the humidity of porous inorganic material again, also special using the three-dimensional space grid structure of inorganic material, with
The organic acid of appropriate architecture phase transition temperature is combined, and realizes temperature adjusting performance.Make temperature adjusting performance, humidity and photocatalysis performance
It is unified, it compensate for single can not really realize of existing product function and improve indoor environment comfort level and improve indoor air quality
Deficiency, improves product competitiveness in the market.
2nd, it is of the invention by palmityl alcohol-palmitic acid-laurate phase-change material and Eu-Ce/TiO2It is compound, not only realize respectively
Palmityl alcohol-palmitic acid-lauric temperature adjusting performance and Eu-Ce/TiO2Humidity, photocatalysis performance；And in material circle
Face realizes heat and mass coupling, further increases comprehensive conditioning performance.Utilize Eu-Ce/TiO simultaneously2Photocatalysis formaldehyde gas
Body produces H2O and moisture pick-up properties, realize humidity enhancing and promote the purpose of light-catalyzed reaction, so as to further improve product
Humidity and photocatalysis performance.
3rd, the present invention meets the policy requirements of national green ecological architectural material, is effectively improved indoor environment comfort level
And changed kind indoor air quality, heating and the use of refrigeration plant, humidifier and air cleaning facility are reduced, reduces and builds
Energy consumption is built, the approach of new function material has been opened up.
Brief description of the drawings
Fig. 1 is indoor environment schematic diagram under HJC-1 type environmental test chamber simulated visible lights source.
In figure：1st, Temperature Humidity Sensor；2nd, thief hatch；3rd, fan；4th, visible light source；A, formaldehyde gas；B, with temperature adjustment
The optic catalytic composite material of humidity.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment, but the present invention is not limited to following embodiments.
First, the preparation of optic catalytic composite material of the present invention with conditioning performance
Embodiment 1
Component used and its quality proportioning are exemplified by preparing product 100g of the present invention：
Phase-change material 10.0g
Catalysis material 90.0g
(1) palmityl alcohol, palmitic acid and lauric mixture are put into container, with constant temperature blender with magnetic force in 2000r/
Mixture is dissolved and stirred under min, 65 DEG C of water bath conditions palmityl alcohol-palmitic acid-laurate phase-change material is obtained after 4h.Institute
Palmityl alcohol, palmitic acid and laurate are stated in palmityl alcohol-palmitic acid-laurate phase-change material by mass fraction ratio 20%:30%:
50%.
(2) matched by butyl titanate with absolute ethyl alcohol volume ratio 2: 5, with constant temperature blender with magnetic force in 1200r/min bars
Obtain homogeneous transparent solution after stirring 30min under part, then by dissolved with the dilute hydrochloric acid solution of europium nitrate and cerous nitrate in 2000r/min
Above-mentioned solution is slowly added under stirring, the pH value for adjusting mixed liquor using watery hydrochloric acid or weak aqua ammonia is 4, in 2000r/min stirrings
Lyosol is obtained after 45min, and ageing indoors forms xerogel, is dried after suction filtration, washing, during then xerogel is put into
600 DEG C are raised to 2 DEG C/min in warm experimental furnace, constant temperature 2h naturally cools to room temperature, obtains Eu-Ce/TiO2Catalysis material,
The Eu-Ce/TiO2Eu-Ce total moles percentage is 1%, Eu and Ce mol ratios 1 in catalysis material：3.
(3) according to the formulation ratio described in claim 1, palmityl alcohol-palmitic acid-laurate phase prepared by step (1)
Become the Eu-Ce/TiO that material is added to step (2) preparation2Mixture is formed in catalysis material.By mixture in 2000r/
The vacuum drying chamber that vacuum is 0.5 standard atmospheric pressure, temperature is 80 DEG C is put into after stirring 30min under min, 65 DEG C of water bath conditions
4h is dried in drying, then natural cooling at ambient, so circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material
Fully absorb palmityl alcohol-palmitic acid-laurate phase-change material.Finally Eu-Ce/TiO is washed using absolute ethyl alcohol2Catalysis material
Palmityl alcohol-palmitic acid-laurate phase-change material of remained on surface, obtains the optic catalytic composite material with conditioning performance.
Embodiment 2
Component used and its quality proportioning are exemplified by preparing product 100g of the present invention：
Phase-change material 15.0g
Catalysis material 85.0g
(1) palmityl alcohol, palmitic acid and lauric mixture are put into container, with constant temperature blender with magnetic force in 2000r/
Mixture is dissolved and stirred under min, 65 DEG C of water bath conditions palmityl alcohol-palmitic acid-laurate phase-change material is obtained after 4h.Institute
Palmityl alcohol, palmitic acid and laurate are stated in palmityl alcohol-palmitic acid-laurate phase-change material by mass fraction ratio 40%:20%:
40%.
(2) matched by butyl titanate with absolute ethyl alcohol volume ratio 2: 5, with constant temperature blender with magnetic force in 1200r/min bars
Obtain homogeneous transparent solution after stirring 30min under part, then by dissolved with the dilute hydrochloric acid solution of europium nitrate and cerous nitrate in 2000r/min
Above-mentioned solution is slowly added under stirring, the pH value for adjusting mixed liquor using watery hydrochloric acid or weak aqua ammonia is 5, in 2000r/min stirrings
Lyosol is obtained after 45min, and ageing indoors forms xerogel, is dried after suction filtration, washing, during then xerogel is put into
550 DEG C are raised to 2 DEG C/min in warm experimental furnace, constant temperature 2h naturally cools to room temperature, obtains Eu-Ce/TiO2Catalysis material,
The Eu-Ce/TiO2Eu-Ce total moles percentage is 2%, Eu and Ce mol ratios 1 in catalysis material：2.
(3) according to the formulation ratio described in claim 1, palmityl alcohol-palmitic acid-laurate phase prepared by step (1)
Become the Eu-Ce/TiO that material is added to step (2) preparation2Mixture is formed in catalysis material.By mixture in 2000r/
The vacuum drying chamber that vacuum is 0.6 standard atmospheric pressure, temperature is 80 DEG C is put into after stirring 30min under min, 65 DEG C of water bath conditions
4h is dried in drying, then natural cooling at ambient, so circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material
Fully absorb palmityl alcohol-palmitic acid-laurate phase-change material.Finally Eu-Ce/TiO is washed using absolute ethyl alcohol2Catalysis material
Palmityl alcohol-palmitic acid-laurate phase-change material of remained on surface, obtains the optic catalytic composite material with conditioning performance.
Embodiment 3
Component used and its quality proportioning are exemplified by preparing product 100g of the present invention：
Phase-change material 20.0g
Catalysis material 80.0g
(1) palmityl alcohol, palmitic acid and lauric mixture are put into container, with constant temperature blender with magnetic force in 2000r/
Mixture is dissolved and stirred under min, 65 DEG C of water bath conditions palmityl alcohol-palmitic acid-laurate phase-change material is obtained after 4h.Institute
Palmityl alcohol, palmitic acid and laurate are stated in palmityl alcohol-palmitic acid-laurate phase-change material by mass fraction ratio 30%:30%:
40%.
(2) matched by butyl titanate with absolute ethyl alcohol volume ratio 2: 5, with constant temperature blender with magnetic force in 1200r/min bars
Obtain homogeneous transparent solution after stirring 30min under part, then by dissolved with the dilute hydrochloric acid solution of europium nitrate and cerous nitrate in 2000r/min
Above-mentioned solution is slowly added under stirring, the pH value for adjusting mixed liquor using watery hydrochloric acid or weak aqua ammonia is 6, in 2000r/min stirrings
Lyosol is obtained after 45min, and ageing indoors forms xerogel, is dried after suction filtration, washing, during then xerogel is put into
500 DEG C are raised to 2 DEG C/min in warm experimental furnace, constant temperature 2h naturally cools to room temperature, obtains Eu-Ce/TiO2Catalysis material,
The Eu-Ce/TiO2Eu-Ce total moles percentage is 3%, Eu and Ce mol ratios 1 in catalysis material：1.
(3) according to the formulation ratio described in claim 1, palmityl alcohol-palmitic acid-laurate phase prepared by step (1)
Become the Eu-Ce/TiO that material is added to step (2) preparation2Mixture is formed in catalysis material.By mixture in 2000r/
The vacuum drying chamber that vacuum is 0.7 standard atmospheric pressure, temperature is 80 DEG C is put into after stirring 30min under min, 65 DEG C of water bath conditions
4h is dried in drying, then natural cooling at ambient, so circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material
Fully absorb palmityl alcohol-palmitic acid-laurate phase-change material.Finally Eu-Ce/TiO is washed using absolute ethyl alcohol2Catalysis material
Palmityl alcohol-palmitic acid-laurate phase-change material of remained on surface, obtains the optic catalytic composite material with conditioning performance.
Embodiment 4
Component used and its quality proportioning are exemplified by preparing product 100g of the present invention：
Phase-change material 25.0g
Catalysis material 75.0g
(1) palmityl alcohol, palmitic acid and lauric mixture are put into container, with constant temperature blender with magnetic force in 2000r/
Mixture is dissolved and stirred under min, 65 DEG C of water bath conditions palmityl alcohol-palmitic acid-laurate phase-change material is obtained after 4h.Institute
Palmityl alcohol, palmitic acid and laurate are stated in palmityl alcohol-palmitic acid-laurate phase-change material by mass fraction ratio 30%:10%:
60%.
(2) matched by butyl titanate with absolute ethyl alcohol volume ratio 2: 5, with constant temperature blender with magnetic force in 1200r/min bars
Obtain homogeneous transparent solution after stirring 30min under part, then by dissolved with the dilute hydrochloric acid solution of europium nitrate and cerous nitrate in 2000r/min
Above-mentioned solution is slowly added under stirring, the pH value for adjusting mixed liquor using watery hydrochloric acid or weak aqua ammonia is 7, in 2000r/min stirrings
Lyosol is obtained after 45min, and ageing indoors forms xerogel, is dried after suction filtration, washing, during then xerogel is put into
450 DEG C are raised to 2 DEG C/min in warm experimental furnace, constant temperature 2h naturally cools to room temperature, obtains Eu-Ce/TiO2Catalysis material,
The Eu-Ce/TiO2Eu-Ce total moles percentage is 4%, Eu and Ce mol ratios 2 in catalysis material：1.
(3) according to the formulation ratio described in claim 1, palmityl alcohol-palmitic acid-laurate phase prepared by step (1)
Become the Eu-Ce/TiO that material is added to step (2) preparation2Mixture is formed in catalysis material.By mixture in 2000r/
The vacuum drying chamber that vacuum is 0.8 standard atmospheric pressure, temperature is 80 DEG C is put into after stirring 30min under min, 65 DEG C of water bath conditions
4h is dried in drying, then natural cooling at ambient, so circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material
Fully absorb palmityl alcohol-palmitic acid-laurate phase-change material.Finally Eu-Ce/TiO is washed using absolute ethyl alcohol2Catalysis material
Palmityl alcohol-palmitic acid-laurate phase-change material of remained on surface, obtains the optic catalytic composite material with conditioning performance.
Embodiment 5
Component used and its quality proportioning are exemplified by preparing product 100g of the present invention：
Phase-change material 30.0g
Catalysis material 70.0g
(1) palmityl alcohol, palmitic acid and lauric mixture are put into container, with constant temperature blender with magnetic force in 2000r/
Mixture is dissolved and stirred under min, 65 DEG C of water bath conditions palmityl alcohol-palmitic acid-laurate phase-change material is obtained after 4h.Institute
Palmityl alcohol, palmitic acid and laurate are stated in palmityl alcohol-palmitic acid-laurate phase-change material by mass fraction ratio 30%:20%:
50%.
(2) matched by butyl titanate with absolute ethyl alcohol volume ratio 2: 5, with constant temperature blender with magnetic force in 1200r/min bars
Obtain homogeneous transparent solution after stirring 30min under part, then by dissolved with the dilute hydrochloric acid solution of europium nitrate and cerous nitrate in 2000r/min
Above-mentioned solution is slowly added under stirring, the pH value for adjusting mixed liquor using watery hydrochloric acid or weak aqua ammonia is 8, in 2000r/min stirrings
Lyosol is obtained after 45min, and ageing indoors forms xerogel, is dried after suction filtration, washing, during then xerogel is put into
400 DEG C are raised to 2 DEG C/min in warm experimental furnace, constant temperature 2h naturally cools to room temperature, obtains Eu-Ce/TiO2Catalysis material,
The Eu-Ce/TiO2Eu-Ce total moles percentage is 5%, Eu and Ce mol ratios 3 in catalysis material：1.
(3) according to the formulation ratio described in claim 1, palmityl alcohol-palmitic acid-laurate phase prepared by step (1)
Become the Eu-Ce/TiO that material is added to step (2) preparation2Mixture is formed in catalysis material.By mixture in 2000r/
The vacuum drying chamber that vacuum is 0.9 standard atmospheric pressure, temperature is 80 DEG C is put into after stirring 30min under min, 65 DEG C of water bath conditions
4h is dried in drying, then natural cooling at ambient, so circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material
Fully absorb palmityl alcohol-palmitic acid-laurate phase-change material.Finally Eu-Ce/TiO is washed using absolute ethyl alcohol2Catalysis material
Palmityl alcohol-palmitic acid-laurate phase-change material of remained on surface, obtains the optic catalytic composite material with conditioning performance.
The chemical reagent that in above-mentioned preparation embodiment 1~5 prepared by palmityl alcohol-palmitic acid-laurate phase-change material：Palm
Alcohol, palmitic acid and laurate are that chemistry is pure；Eu-Ce/TiO2Chemical reagent prepared by catalysis material：Butyl titanate is change
Learn pure, hydrochloric acid, ammoniacal liquor, europium nitrate, cerous nitrate, absolute ethyl alcohol are that chemistry is pure.
The optic catalytic composite material sample with conditioning performance for preparing embodiment 1~5 carries out temperature adjusting performance, damping
Performance and air cleaning performance detection, its process are as follows：
1st, the temperature adjusting performance test of composite of the present invention
Optic catalytic composite material with conditioning performance is tested using the type differential scanning calorimeters of U.S. TA 2910
Phase transition temperature and enthalpy of phase change.The phase transition temperature and enthalpy of phase change of optic catalytic composite material embodiment 1~5 with conditioning performance
It is included in table 1.
Table 1 has the phase transition temperature and enthalpy of phase change of the optic catalytic composite material of conditioning performance
2nd, the humidity test of composite of the present invention
The sample that size is 50mm × 50mm × 5mm is made in optic catalytic composite material with conditioning performance, is put
Enter in the weighing cup through drying process and weighing (not tea cup with a cover lid), be put into vacuum drying chamber and dry.Contained in drier into conjunction
Suitable saturated salt solution (being shown in Table 2), makes the humidity needed for maintaining in drier, then will dry to the sample of constant weight and weigh note
Record, weighing cup (not tea cup with a cover lid) is respectively put into the drier of different relative humidity.Periodically weigh until before and after sample mass
Change is met untill requiring (difference before and after quality is not more than 0.01%).Similarly, successively decrease according to humidity and carried out moisture releasing process
Experiment, until moisture releasing process terminates.The equilibrium moisture content of sample is u, and formula is shown in its calculating：
In formula：m0For the quality of sample under drying regime, g；M is the sample mass after moisture adsorption and releasing, g.
The equilibrium moisture content of optic catalytic composite material embodiment 1~5 with conditioning performance is included in table 3.
The different relative humidity saturated solutions of table 2 are with tabulation (25 DEG C)
Table 3 has the equilibrium moisture content of the optic catalytic composite material of conditioning performance
3rd, the air cleaning performance test of composite of the present invention
Indoor environment (as shown in Figure 1) under the HJC-1 type environmental test chamber simulated visible lights source generally used using European Union.
Using Temperature Humidity Sensor 1, temperature setting is at 23 ± 0.5 DEG C, and humidity is arranged on 45 ± 3%.2.5 μ L concentration be 37%~
40% formaldehyde is analyzed pure solution and is added dropwise on culture dish, is put into environmental test chamber, it is fully volatilized in environmental test chamber,
It is 1mg/m to make the formaldehyde gas a concentration in whole environmental test chamber using fan 33.By the tool of theoretical coating thickness (200 μm)
The optic catalytic composite material b for having conditioning performance loads to 0.1m2Glass on, excited using visible light source 4, make it
Produce photocatalysis.Using acetylacetone,2,4-pentanedione AAS (GB/T15516-1995), using thief hatch 2, selection every
The change in concentration of formaldehyde gas, has so as to calculate in gas in 60min sampling 10L cabins, detection environmental test chamber
The efficiency of the optic catalytic composite material Photo-Catalytic Degradation of Formaldehyde of conditioning performance.
The Photo-Catalytic Degradation of Formaldehyde efficiency row of optic catalytic composite material embodiment 1~5 with conditioning performance
Enter table 4.
Table 4. has the Photo-Catalytic Degradation of Formaldehyde efficiency (%) of the optic catalytic composite material of conditioning performance
Claims (1)
1. a kind of optic catalytic composite material with conditioning performance, it is characterised in that the composite is by mass percentage
Formula is as follows：
Phase-change material 10~30
Catalysis material 70~90
The phase-change material is palmityl alcohol, palmitic acid and lauric mixture, and its phase transition temperature is 21.0 DEG C~30.0 DEG C；Institute
Catalysis material is stated for Eu-Ce/TiO2, its particle diameter is 180nm~220nm；
The preparation of the optic catalytic composite material with conditioning performance comprises the following steps：
(1) preparation of palmityl alcohol-palmitic acid-laurate phase-change material：Palmityl alcohol, palmitic acid and lauric mixture are put into
In container, obtained with constant temperature blender with magnetic force under 2000r/min, 65 DEG C of water bath conditions by mixture dissolving and after stirring 4h
Palmityl alcohol-palmitic acid-laurate phase-change material；Palmityl alcohol, palmitic acid in the palmityl alcohol-palmitic acid-laurate phase-change material
It is 20~40 with lauric mass fraction ratio:10~30:40~60；
(2)Eu-Ce/TiO2The preparation of catalysis material：Matched by butyl titanate and absolute ethyl alcohol volume ratio 2: 5, use constant temperature magnetic
Power agitator obtains homogeneous transparent solution under the conditions of the 1200r/min after stirring 30min, then by dissolved with europium nitrate and cerous nitrate
Dilute hydrochloric acid solution adjusts the pH of mixed liquor using watery hydrochloric acid or weak aqua ammonia in being slowly added to above-mentioned solution under 2000r/min stirrings
It is worth for 4~8, lyosol is obtained after 2000r/min stirrings 45min, and ageing forms xerogel, suction filtration, washing indoors
After dry, then xerogel is put into middle temperature experimental furnace 400 DEG C~600 DEG C, constant temperature 2h, natural cooling is raised to 2 DEG C/min
To room temperature, Eu-Ce/TiO is obtained2Catalysis material；The Eu-Ce/TiO2Eu-Ce total moles percentage is in catalysis material
1%~5%, Eu and Ce mol ratios 3~1：1~3；
(3) preparation of the optic catalytic composite material with conditioning performance：According to above-mentioned formulation ratio, prepared by step (1)
Palmityl alcohol-palmitic acid-laurate phase-change material be added to step (2) preparation Eu-Ce/TiO2Formed in catalysis material mixed
Compound, mixture is stirred under 2000r/min, 65 DEG C of water bath conditions be put into after 30min vacuum for 0.5 standard atmospheric pressure~
0.9 standard atmospheric pressure, temperature are dried for 80 DEG C of vacuum drying chamber and 4h are dried, then natural cooling at ambient, so
Circulation more than 2 times, it is ensured that Eu-Ce/TiO2Catalysis material fully absorbs palmityl alcohol-palmitic acid-laurate phase-change material, finally
Eu-Ce/TiO is washed with absolute ethyl alcohol2Palmityl alcohol-palmitic acid-laurate phase-change material of catalysis material remained on surface, is obtained
Target product：Optic catalytic composite material with conditioning performance.
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| CN103992773A (en) * | 2014-05-28 | 2014-08-20 | 北京化工大学常州先进材料研究院 | Bifunctional micro-encapsulation phase-change energy storage material with photo-catalysis property and preparation method thereof |
| CN104449591A (en) * | 2014-12-10 | 2015-03-25 | 西安建筑科技大学 | Nanoscale dibasic fatty acid/SiO2 composite phase change material having temperature-regulating and humidity-regulating properties and preparation method thereof |
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| CN103865303A (en) * | 2014-04-03 | 2014-06-18 | 安徽工业大学 | Fire-retardant coating with photo-catalytic performance and preparation method thereof |
| CN103992773A (en) * | 2014-05-28 | 2014-08-20 | 北京化工大学常州先进材料研究院 | Bifunctional micro-encapsulation phase-change energy storage material with photo-catalysis property and preparation method thereof |
| CN104449591A (en) * | 2014-12-10 | 2015-03-25 | 西安建筑科技大学 | Nanoscale dibasic fatty acid/SiO2 composite phase change material having temperature-regulating and humidity-regulating properties and preparation method thereof |
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