CN109759080A - Oxidation of formaldehyde composite catalyzing material and preparation method thereof - Google Patents
Oxidation of formaldehyde composite catalyzing material and preparation method thereof Download PDFInfo
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- CN109759080A CN109759080A CN201910047744.1A CN201910047744A CN109759080A CN 109759080 A CN109759080 A CN 109759080A CN 201910047744 A CN201910047744 A CN 201910047744A CN 109759080 A CN109759080 A CN 109759080A
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- oxidation
- formaldehyde
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 17
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 15
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229940009827 aluminum acetate Drugs 0.000 claims abstract description 15
- 235000019253 formic acid Nutrition 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 229940060038 chlorine Drugs 0.000 claims abstract description 7
- 230000009975 flexible effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 23
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 13
- 229910021277 Co3O4-Al2O3 Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 241001391944 Commicarpus scandens Species 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001523 electrospinning Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of oxidation of formaldehyde composite catalyzing materials and preparation method thereof, solve the problems such as easy to break, flexibility differential thermal stability is poor, preparation method is complicated existing for existing formaldehyde catalysis material.The method of the present invention is that formic acid and acetic acid are first dissolved in water, then sequentially adds aluminum acetate, cobalt acetate and chlorine palladium acid sodium, and stirring forms clear solution, the polyethylene glycol oxide of 0.25~1.25wt% of the clear solution gross mass is then added, is uniformly mixing to obtain mixed liquor；Electrostatic spinning is carried out to the mixed liquor and obtains the composite cellulosic membrane of high molecular nanometer containing Pd；To contain Pd high molecular nanometer composite cellulosic membrane roasted, be activated after obtain.The method of the present invention is simple and reliable, operation difficulty is low, with short production cycle, and catalyst material obtained is flexible film-like, has the advantages that catalytic activity is high, thermal stability is good, flexibility is good, is not easily broken, is not easily to fall off.
Description
Technical field
The present invention relates to belong to inorganic nano combined catalysis material preparation technical field, specifically a kind of oxidation of formaldehyde
Composite catalyzing material and preparation method thereof.
Background technique
Formaldehyde is one of most important pollutant in room air, and the formaldehyde removed in room air is that people make the life better
The urgent need of quality.Room temperature catalytic oxidation method is the hot subject for removing formaldehyde in indoor air in recent years, it has reaction
The advantages that mild condition (carrying out under normal temperature and pressure), removal efficiency are high, and the service life is long, application potential is huge.In recent years, which exists
Have numerous studies and report in indoor air purification, as Chinese invention patent CN200410047973.7,
CN200410102837.3、CN200910215887.5、CN200910098634.4、CN200910047376.7、
CN200610011663.9, CN200710121423.9, CN201210389227.0 and CN201410015867.4.Patent
CN201210389227.0 reports a kind of preparation method of formaldehyde room temperature oxidation catalyst, and this method is inorganic with powdery porous
Oxide is carrier, and using sodium borohydride as reducing agent, soluble metal hydroxide is additive, passes through dipping-room temperature reduction-
Sedimentation and noble metal precursor precursor reactant are made.But the catalyst prepared in patent disclosed above be mostly it is powdered, from practical
From the point of view of, these catalyst, which are such as applied in filled-type cleaning equipment, to be needed tabletting or is further supported on other big
It could be used on block type carrier, this can make process complications, and there are catalytic activity decline and the caducous problems of catalyst.For
Overcome drawbacks described above, the TiO that patent CN201410015867.4 is prepared with method of electrostatic spinning2For carrier, also with dipping~room temperature
Original~deposition two step method is prepared for carried noble metal/TiO2The catalyst of composite catalyst, this method preparation can be used directly,
But inorganic TiO in the catalyst2Nanofiber has fragility, can constantly be broken off during making and using, original
Fibre structure is gradually corrupted such that catalytic activity will receive influence, and two-step method can be such that processing step complicates, and increase behaviour
Make difficulty, extend the production cycle.
Summary of the invention
The purpose of the present invention is to solve above-mentioned technical problem, provide that a kind of catalytic activity is high, thermal stability is good, is not easy
The flexible film-like oxidation of formaldehyde composite catalyzing material to fracture.
The present invention also provides a kind of simple processes, the oxidation of formaldehyde composite catalyzing material that production difficulty is low, with short production cycle
Preparation method.
The method of the present invention the following steps are included:
(1): formic acid and acetic acid being first dissolved in water, then sequentially add aluminum acetate, cobalt acetate and chlorine palladium acid sodium, stirring is formed
Clear solution, wherein the molar ratio of each raw material are as follows: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=1:0.2~
0.4:0.1~0.2:0.03~0.6:0.001~0.005:(0.642~6.42) × 10-4；
(2) polyethylene glycol oxide of 0.25~1.25wt% of the clear solution gross mass is then added, is uniformly mixing to obtain
Mixed liquor；
(3) electrostatic spinning is carried out to the mixed liquor and obtains the composite cellulosic membrane of high molecular nanometer containing Pd；
(4) will contain Pd high molecular nanometer composite cellulosic membrane roasted, be activated after obtain.
In the step (2), polyethylene glycol oxide molecular weight is between 30~600,000.
In the step (3), the flow velocity of electrostatic spinning is 1~2mL/h, and spinning needle diameter is 0.5~1mm, work
Voltage strength is 1~2kV/cm；Relative humidity controls below 20%.
In the step (3), 1.2~1.5mL/h of flow velocity of electrostatic spinning liquid, spinning needle diameter is 0.7~0.9mm,
Operating voltage intensity is 1.1~1.3kV/cm；Relative humidity controls below 10%.
In the step (4), maturing temperature is 500-700 DEG C, calcining time 1-4h, and heating rate is 1-2 DEG C/min.
In the step (4), the activation method are as follows: in H2Calcining matter is handled into 0.5- at 200-250 DEG C in atmosphere
2h。
Oxidation of formaldehyde composite catalyzing material of the present invention, is made by above-mentioned preparation method, is Pd@Co3O4/γ-Al2O3Fiber
Oxidation of formaldehyde composite catalyzing material.
Pd@Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material contains γ-Al2O3Fiber carrier, Co3O4It helps and urges
Agent ingredient and the Pd active component for being dispersed in carrier surface, wherein Pd exists in the form of zeroth order, 1~10nm of particle size range；Tool
There is graduation macropore-central hole structure, aperture is in 1~1000nm.
The Pd@Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material is fexible film made of fiber interweaving
Shape, film thickness is at 80~110 μm, tensile stress are as follows: 16~30Mpa, thermostabilization is at 500~700 DEG C.For in background technique
There are the problem of, inventor improves raw material and technical process, on the one hand, aluminum acetate and cobalt acetate are added in raw material,
With formic acid, acetic acid together as spinning presoma, in stirring early period ageing process can by intermolecular dehydration and
Chemical bond and crosslink and polymerization process, the strong chemical bond in this polymerization process acts on electrostatic spinning and roasted
Cheng Zhongneng is maintained, and therefore, high temperature resistant can be obtained after finally roasting, is not easily broken, film-shaped catalyst flexible, is solved
Existing catalyst brittleness is high in background technique, easy to break in the production and use process, influence the problem of catalytic activity；
On the other hand, inventor just joined presoma chlorine palladium acid sodium, during electrostatic spinning, Pd before electrostatic spinning
Presoma can move to carrier surface with the volatilization of moisture, for impregnating-depositing again after relatively baking, active component Pd group
It point can preferably disperse in the carrier, then be baked process, make to combine between Pd and carrier more secured, solve activity on carrier
The disadvantages of component is easy to fall off, poor catalyst stability；Through H2The Pd nano particle of 0 valence of high dispersive can be obtained after reduction, 0 valence
Pd can have a preferable formaldehyde room temperature oxidation activity, and Co3O4In Co element there is variable valence state, facilitate Pd and generate more
More active oxygen species, therefore catalytic performance can be further increased.
Further, the molar ratio of each raw material should control: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=
1:(0.2~0.4): (0.1~0.2): (0.03~0.6): (0.001~0.005): (0.642~6.42) × 10-4, wherein vinegar
Acid-aluminum ratio is worth the excessively high Co that will affect3O4Promoting catalysis, it is too low to influence whether film flexibility；Cobalt acetate ratio is excessively high can shadow
It rings and arrives film flexibility, too low to influence whether its promoting catalysis, chlorine palladium acid sodium ratio is excessively high can the easy reunion of Pd nanoparticle
Become larger, influences catalytic activity, it is too low to influence whether activated centre quantity, and then influence catalytic activity.
Compared with prior art, the invention has the following beneficial effects:
(1) catalyst of the invention is inorganic material composite construction, is firmly combined between Pd and carrier, while having graduation
Mesoporous-macroporous structure, aperture are highly dispersed at Co in 1~1000nm, active component Pd component3O4/γ-Al2O3Fiber surface,
Partial size is between 1-10nm and is 0 valence, and room temperature can efficiently catalyzing and oxidizing formaldehyde；
(2) catalyst of the present invention is shaped to film-form by fiber interweaving, have it is flexible, intensity is high, thermal stability is good,
The advantages that not easily to fall off, may be directly applied in various filled-type cleaning equipments, can avoid traditional catalyst and is applied to filled-type
It needs tabletting in cleaning equipment or is further supported on other bulk type carriers to use and that there are catalyst is easily de-
The problem of falling also can avoid as TiO2Inorganic nano-fiber is that the composite catalyzing material of carrier exists during making and using
The problem of frangibility；
(3) one-step method is used, all raw materials are blended electrostatic spinning after dissolution, bake obtained, simple process, easily operated,
It is with short production cycle, reproducible, it is suitble to industrialized production.
(4) composite catalyzing strength of materials height provided by the present invention and high temperature resistant, are suitable for all kinds of air purifiers, both may be used
It is catalyzed and reacts for formaldehyde room temperature, it can also be used to other high temperature heterogeneous catalytic reactions, such as removing of other VOCs, CH4Oxidation, CO
Oxidation, O3Removing etc., it is applied widely.
Detailed description of the invention
Fig. 1 is Pd@Co prepared by embodiment 33O4/γ-Al2O3The optical photograph of fiber oxidation of formaldehyde composite catalyzing material.
Fig. 2 is Pd@Co prepared by embodiment 33O4/γ-Al2O3The scanning electron of fiber oxidation of formaldehyde composite catalyzing material
Microscope figure.
Fig. 3 is Pd@Co prepared by embodiment 33O4/γ-Al2O3The XPS spectrum figure of fiber oxidation of formaldehyde composite catalyzing material.
Specific embodiment
Below in conjunction with specific embodiments of the present invention, the present inventor's content is done and is further described, but this
The protection scope of invention is not limited to these examples.It is all to be included in without departing substantially from the change of present inventive concept or equivalent substitute
Within protection scope of the present invention.
Embodiment 1
(1) formic acid and acetic acid are dissolved in water, then sequentially add aluminum acetate, cobalt acetate and chlorine palladium acid sodium, stirring forms saturating
Bright solution, wherein the molar ratio of each substance are as follows: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=1:0.2:0.15:
0.04:0.002:1.28 × 10-4；Then it is 0.25wt% polyethylene glycol oxide (molecular weight 600,000) that its percent concentration, which is added, is stirred
6h is mixed, after uniform, carrying out electrostatic spinning, (electrospinning conditions: the flow velocity 1mL/h of spinning solution, spinning needle diameter are 1mm, work
Making voltage strength is 1.2kV/cm；Relative humidity is controlled 10%.) composite cellulosic membrane of high molecular nanometer containing Pd is obtained, then will
For gained polymer composite in 500 DEG C of roasting 2h, heating rate is 1 DEG C/min.Finally, in H2200 DEG C of processing 0.5h in atmosphere,
Obtain Pd@Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material.
Embodiment 2
Formic acid and acetic acid are dissolved in water, then sequentially add aluminum acetate, cobalt acetate and chlorine palladium acid sodium, stirring forms transparent molten
Liquid, wherein the molar ratio of each substance are as follows: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=1:0.3:0.1:0.03:
0.001:0.642 × 10-4；Then it is 0.5wt% polyethylene glycol oxide (molecular weight 500,000) that its percent concentration, which is added, and stirring 8h is equal
After even, carrying out electrostatic spinning, (electrospinning conditions: the flow velocity 2mL/h of spinning solution, spinning needle diameter are 0.7mm, operating voltage
Intensity is 1kV/cm；Relative humidity is controlled 20%.) composite cellulosic membrane of high molecular nanometer containing Pd is obtained, then it will be secured satisfactory grades
For sub- compound in 600 DEG C of roasting 2h, heating rate is 1 DEG C/min.Finally, in H2250 DEG C of processing 1h, obtain Pd@in atmosphere
Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material.
Embodiment 3
Formic acid and acetic acid are dissolved in water, then sequentially add aluminum acetate, cobalt acetate and chlorine palladium acid sodium, stirring forms transparent molten
Liquid, wherein the molar ratio of each substance are as follows: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=1:0.3:0.2:0.06:
0.005:2.56 × 10-4；Then it is 0.25wt% polyoxyethylene glycol (molecular weight 500,000) that its percent concentration, which is added, stirs 12h
After uniformly, carrying out electrostatic spinning, (electrospinning conditions: the flow velocity 1.5mL/h of spinning solution, spinning needle diameter are 1mm, work electricity
Compressive Strength is 2kV/cm；Relative humidity controls below 15%.) composite cellulosic membrane of high molecular nanometer containing Pd is obtained, then by institute
Sub- compound secure satisfactory grades in 700 DEG C of roasting 1h, heating rate is 1.5 DEG C/min.Finally, in H2200 DEG C of processing 2h, obtain in atmosphere
To Pd@Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material.
It prepares sample topography and sees Fig. 1, be film-form；Fig. 2 stereoscan photograph is shown, and the film is by a large amount of fiber interweavings
It forms, there is graduation mesoporous-macroporous structure between fiber.XPS characterization result shows that Pd is 0 valence (see Fig. 3).Another transmission electron microscope
Show that Pd particle diameter distribution is about 4~6nm.
Embodiment 4
Formic acid and acetic acid are dissolved in water, then sequentially add aluminum acetate, cobalt acetate and chlorine palladium acid sodium, stirring forms transparent molten
Liquid, wherein the molar ratio of each substance are as follows: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=1:0.4:0.2:0.03:
0.001:6.42 × 10-4；Then it is 1.25wt% polyethylene glycol oxide (molecular weight 300,000) that its percent concentration, which is added, and stirring 6h is equal
After even, carrying out electrostatic spinning, (electrospinning conditions: the flow velocity 1mL/h of spinning solution, spinning needle diameter are 0.5mm, operating voltage
Intensity is 1.5kV/cm；Relative humidity is controlled 20%.) composite cellulosic membrane of high molecular nanometer containing Pd is obtained, then by gained height
For molecular complex in 500 DEG C of roasting 4h, heating rate is 1.5 DEG C/min.Finally, in H2230 DEG C of processing 1h, obtain in atmosphere
Pd@Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material.
Comparative example 5
In addition to chlorine palladium acid sodium is not added, other experimentations are identical with embodiment 3.Finally obtain Co3O4/γ-
Al2O3Composite material.
Comparative example 6
In addition to cobalt acetate is not added, other experimentations are identical with embodiment 3.Finally obtain Pd/ γ-Al2O3Fiber
Oxidation of formaldehyde composite catalyzing material.
Comparative example 7
For catalyst material made from the disclosed embodiment of Patent No. CN201410015867.4 described in background technique 1
Material.
Table 1
Table 2
From Table 2, it can be seen that the tensile stress of sample prepared in the present invention is greater than with electrostatic spinning TiO2Fiber
For the tensile stress of the catalysis material of carrier two-step method preparation, therefore the former shows better flexibility, is not easily broken, then
The fragility of person's performance.Meanwhile prepared catalysis material shows good thermal stability in the present invention.
Formaldehyde room temperature oxidation test
Test process is as follows: prepared catalyst sample being placed in 6L reactor, then concentrated formaldehyde solution is injected instead
It answers in device, opens fan, until formaldehyde volatilization is until concentration balance, glass cover is removed, catalyst starts to contact with formaldehyde at this time
The concentration variation of formaldehyde and product carbon dioxide is monitored in reaction on-line by Multi-Component Gas Analyzing instrument in the process.
The activity data of Examples 1 to 4 and the catalyst of embodiment 5-7 preparation in 60min is shown in Table 3.As known from Table 3,
Catalyst of the invention all has good catalytic activity.The sample prepared in comparative example 5 then formaldehydeless oxidation activity.
Illustrate that Pd is the chief active species of oxidation of formaldehyde.The sample prepared in comparative example 6 is generated than sample prepared by embodiment 3
CO2It is few, show the low and Co of activity3O4Presence have conducive to active raising, play the role of co-catalyst.
Table 3
The another repeat performance to investigate catalyst of the present invention, the special catalyst sample by embodiment 3 reuse 4
It is secondary, its Repeatability is observed, the results are shown in Table 4, as seen from Table 4: catalyst of the invention is in multiple use process, activity
It is held essentially constant, illustrates that catalyst activity of the present invention is stablized.Although the catalysis material prepared in the embodiment of the present invention 3 and comparison
The activity of the Pt catalysis material prepared in example 7 wants lower, and the Pt ratio Pd of main cause is more preferable to the activation capacity of oxygen, but its is flexible
Property has obtained significant raising (being shown in Table 2).
Table 4
Claims (9)
1. a kind of preparation method of oxidation of formaldehyde composite catalyzing material, which comprises the following steps:
(1): formic acid and acetic acid being first dissolved in water, then sequentially add aluminum acetate, cobalt acetate and chlorine palladium acid sodium, stirring forms transparent
Solution, wherein the molar ratio of each raw material are as follows: water: formic acid: acetic acid: aluminum acetate: cobalt acetate: chlorine palladium acid sodium=1:0.2~0.4:0.1
~0.2:0.03~0.6:0.001~0.005:(0.642~6.42) × 10-4；
(2) polyethylene glycol oxide of 0.25~1.25wt% of the clear solution gross mass is then added, is uniformly mixing to obtain mixing
Liquid；
(3) electrostatic spinning is carried out to the mixed liquor and obtains the composite cellulosic membrane of high molecular nanometer containing Pd；
(4) will contain Pd high molecular nanometer composite cellulosic membrane roasted, be activated after obtain.
2. the preparation method of oxidation of formaldehyde composite catalyzing material as described in claim 1, which is characterized in that the step (2)
In, polyethylene glycol oxide molecular weight is between 30~600,000.
3. the preparation method of oxidation of formaldehyde composite catalyzing material as described in claim 1, which is characterized in that the step (3)
In, the flow velocity of electrostatic spinning is 1~2mL/h, and spinning needle diameter is 0.5~1mm, and operating voltage intensity is 1~2kV/cm；
Relative humidity controls below 20%.
4. the preparation method of oxidation of formaldehyde composite catalyzing material as claimed in claim 3, which is characterized in that the step (3)
In, 1.2~1.5mL/h of flow velocity of electrostatic spinning liquid, spinning needle diameter be 0.7~0.9mm, operating voltage intensity be 1.1~
1.3kV/cm；Relative humidity controls below 10%.
5. the preparation method of oxidation of formaldehyde composite catalyzing material according to any one of claims 1-4, which is characterized in that described
In step (4), maturing temperature is 500-700 DEG C, calcining time 1-4h, and heating rate is 1-2 DEG C/min.
6. the preparation method of oxidation of formaldehyde composite catalyzing material according to any one of claims 1-4, which is characterized in that described
In step (4), the activation method are as follows: in H2Calcining matter is handled into 0.5-2h at 200-250 DEG C in atmosphere.
7. a kind of oxidation of formaldehyde composite catalyzing material, which is characterized in that by the described in any item preparation method systems of claim 1-5
, it is Pd@Co3O4/γ-Al2O3Fiber oxidation of formaldehyde composite catalyzing material.
8. oxidation of formaldehyde composite catalyzing material as claimed in claim 7, which is characterized in that Pd@Co3O4/γ-Al2O3Fiber first
Oxidation of aldehydes composite catalyzing material contains γ-Al2O3Fiber carrier, Co3O4Co-catalyst component and the Pd for being dispersed in carrier surface are living
Property component, wherein Pd exists in the form of zeroth order, 1~10nm of particle size range；With graduation macropore-central hole structure, aperture 1~
1000nm。
9. oxidation of formaldehyde composite catalyzing material as claimed in claim 8, which is characterized in that the Pd@Co3O4/γ-Al2O3It is fine
Tieing up composite formaldehyde catalysis material is flexible film-like made of fiber interweaving, and film thickness is at 80~110 μm, tensile stress are as follows:
16~30Mpa, thermostabilization exist: 500~700 DEG C.
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