CN107138153A - The carbon fiber felt of growth in situ load stratiform manganese oxide and its synthetic method and application - Google Patents
The carbon fiber felt of growth in situ load stratiform manganese oxide and its synthetic method and application Download PDFInfo
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- CN107138153A CN107138153A CN201710271860.2A CN201710271860A CN107138153A CN 107138153 A CN107138153 A CN 107138153A CN 201710271860 A CN201710271860 A CN 201710271860A CN 107138153 A CN107138153 A CN 107138153A
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- carbon fiber
- fiber felt
- manganese oxide
- stratiform
- acid
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 127
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 115
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 115
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 90
- 230000003647 oxidation Effects 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 239000008236 heating water Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- 238000002203 pretreatment Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 31
- 239000003054 catalyst Substances 0.000 description 27
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910006364 δ-MnO2 Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PQQBWLKXIHCGRL-UHFFFAOYSA-N [O-2].[Mn+2].[C+4].[O-2].[O-2] Chemical compound [O-2].[Mn+2].[C+4].[O-2].[O-2] PQQBWLKXIHCGRL-UHFFFAOYSA-N 0.000 description 2
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910003179 MnxCo3−xO4 Inorganic materials 0.000 description 1
- -1 Na+ Chemical class 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 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 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The present invention relates to the carbon fiber felt of growth in situ load stratiform manganese oxide and its synthetic method and application, the carbon fiber felt material of the load stratiform manganese oxide, include the δ phase oxidation manganese nanometer sheets of carbon fiber felt and the growth in situ carbon fiber surface in the carbon fiber felt, the δ phase oxidations manganese nanometer sheet has layered crystal structure.The present invention uses nitric acid pre-treatment carbon fiber felt carrier, reacted in acid condition with the carbon fiber felt after activation by liquor potassic permanganate again, in-situ preparation is carried on the oxidation manganese material on carbon fiber mountain, and this method has simple and easy to apply, it is environment-friendly, the features such as with low cost.
Description
Technical field
The invention belongs to environmental catalysis field, it is related to a kind of carbon fiber felt material for loading stratiform manganese oxide, more particularly to
A kind of new, green, efficient crystallization catalyst and its preparation method and application as catalytic oxidation of low-concentration formaldehyde.
Background technology
In recent years, because the cheap industrial chemicals such as phenolic resin, Lauxite is added into coating and sheet material bonding extensively
In the products such as agent, Formaldehyde Pollution of Indoor Air problem is increasingly serious.It is well known that formaldehyde has strong impulse, it is that a kind of teratogenesis is caused
Cancer thing.Therefore, for health, formaldehyde is removed imperative.
At present, the Main Means of formaldehyde are removed at room temperature includes absorption, plasma oxidation, catalysis oxidation (burning), light
Catalysis oxidation etc..Heat catalytic oxidation method is into CO using dynamical catalyst by VOCs catalytic degradations2And H2O, it has catalysis
The advantages of efficiency high, non-secondary pollution, easily-controlled operation, be a kind of technology of great prospect.Catalyst for removing VOCs
Mainly there are two kinds of catalyst of transition metal oxide and noble-metal-supported catalyst.Common transition group metallic oxide catalyst
There is Co3O4、MnOx、CeO2Deng.Noble metal catalyst has platinum, palladium, gold, silver etc., and they are generally loaded on transition metal oxide
Or on their mixture.Compared to noble metal catalyst, transition group metallic oxide catalyst substantially has cheap, storage
The advantages of measuring many.
In numerous transition metal oxides, the oxide of manganese is widely used in many due to the characteristic such as cheap, nontoxic
In catalytic reaction, such as CO oxidations.In numerous crystal formations of manganese oxide, especially using Birnessite be δ-MnO2 catalytic effect as
Good, it is a number of hydrone and difference between the layer structure formed by group of MnO6 regular octahedrons, manganese oxide layer that it, which is,
Cation (such as Na+, K+, Ca2+).Layer structure unique Birnessite become an effective catalyst by with
In removal carbon monoxide and VOC (VOC).Open and wait (Zhang J, Li Y, Wang L, et
al.Catalytic oxidation of formaldehyde over manganese oxides with different
crystal structures[J].Catalysis Science&Technology,2015,5(4):2305-2313.) find
δ-MnO2 catalyst has higher catalytic activity when removing formaldehyde than α, β and γ-MnO2.
Active-carbon fibre material is unusual one of popular material in recent years, and it is by organic fibers such as flake graphites
Pile up and form along fiber axial direction, with microcellular structure, relatively high specific surface area, abundant surface group is conducive to first
The absorption of aldehyde gas, using the teaching of the invention it is possible to provide sufficient space and avtive spot scattered enough.
Formaldehyde is a kind of typical harmful organic compounds.On the one hand, it is harmful to environment and human body, can cause fiber crops
Liquor-saturated disease and increase photochemical pollution.On the other hand, certainly, catalysis oxidation strategy is a kind of most potential in room
The method that the lower high efficiency of temperature removes formaldehyde.Apply et al. and to find that MnxCo3-xO4 catalyst can be with complete catalysts oxidation first at 75 DEG C
Aldehyde, and catalyst life was up to 50 hours.Week et al., (Zhou Xinyan, a Peng, Jiang Wen, waited Mn oxides modified activated carbon to remove
Formaldehyde in air [J] environmental project journals, 2015,9 (12):5965-5972.) MnOx/GAC is successfully prepared by infusion process
Catalyst, the formaldehyde in air is adsorbed using the huge specific surface area of activated carbon, the catalytic reaction efficiency of Mn oxide is improved.
But the acticarbon used is the problem of easily cause secondary pollution.
The content of the invention
In view of the above-mentioned problems, object of the present invention is to provide a kind of catalyst of new removal low concentration formaldehyde and
Its preparation method and application.
On the one hand, the invention provides it is a kind of load stratiform manganese oxide carbon fiber felt material, including carbon fiber felt and
The δ phase oxidation manganese nanometer sheets of growth in situ carbon fiber surface in the carbon fiber felt, the δ phase oxidations manganese nanometer sheet has layer
Shape crystal structure.
The carbon fiber felt material of heretofore described load stratiform manganese oxide includes：Carbon fiber felt and growth in situ are in institute
State the δ phase oxidation manganese nanometer sheets of carbon fiber surface in carbon fiber felt.Wherein carbon fiber felt as active-carbon fibre material, it be by
The organic fibers such as flake graphite are piled up along fiber axial direction to be formed, rich with microcellular structure, relatively high specific surface area
Rich surface group, is conducive to the absorption of formaldehyde gas, using the teaching of the invention it is possible to provide sufficient space and avtive spot scattered enough.This
Outside, growth in situ δ phase oxidation manganese nanometer sheets of carbon fiber surface in carbon fiber felt have layered crystal structure, can provide more
Many avtive spots are with catalysis formaldehyde more efficiently.In addition, the carbon fiber for having loaded stratiform manganese oxide mentioned by the present invention
Material has different surface oxygen species (surface adsorbed oxygen, carbon fiber surface oxy radical oxygen species and Lattice Oxygen) and certain
Low temperature reducibility (manganese oxide has certain low-temperature reduction, and low-temperature reduction is obtained by H2-TPR experiments, its first
Peak correspondence low-temperature reduction), this is all beneficial to the progress of catalytic oxidation, it is possible to achieve lower at room temperature to remove low concentration
The purpose of formaldehyde.
It is preferred that in the carbon fiber felt material of the load stratiform manganese oxide content of δ phase oxidation manganese nanometer sheets for 21~
24wt%.
It is preferred that the specific surface area of the carbon fiber felt material of the load stratiform manganese oxide is 25.75~47.42m2/g、
A diameter of 14~19nm of mesopore orbit.
On the other hand, present invention also offers a kind of preparation side of the carbon fiber felt material of above-mentioned load stratiform manganese oxide
Method, including：
Carbon fiber felt is pre-processed using acid with strong oxidizing property；
Pretreated carbon fiber felt is impregnated in liquor potassic permanganate, adding a certain amount of acid makes the pH of liquor potassic permanganate extremely
1~2, through being dried at washing, 60~100 DEG C after then being reacted 3~9 hours at 60~80 DEG C, obtain the load stratiform oxygen
Change the carbon fiber felt material of manganese.
The present invention is pre-processed first by acid with strong oxidizing property to carbon fiber felt, it is activated the carbon after (pretreatment) fine
Tieing up material surface has abundant active group (for example, hydroxyl, carboxyl etc.), makes it easier to react with potassium permanganate.Then,
The carbon fibre material that gained is activated after (pretreatment) again is placed in liquor potassic permanganate, and adding a certain amount of hydrochloric acid makes potassium permanganate
The pH of solution to 1~2, carries out heating water bath so that carbon fiber reacts in potassium permanganate and carbon fiber felt：C+2KMnO4=
K2MnO4+MnO2+ CO2 ↑, finally cause stratiform manganese oxide (MnO2) growth in situ in carbon fiber surface, obtain load stratiform oxidation
The carbon fiber felt material of manganese, wherein it is the good stratiform manganese oxide nanometer sheet material of crystallization to be carried on carbon fiber.
It is preferred that carbon fiber felt is placed in acid with strong oxidizing property into heating water bath 3~5 hours at 60~80 DEG C, obtain pre-
Carbon fiber felt after processing.
It is preferred that the acid with strong oxidizing property is selected from nitric acid or/and sulfuric acid, preferably concentration is 69% concentrated nitric acid.
It is preferred that the mass ratio of carbon fiber felt and potassium permanganate is (2~4)：10.
It is preferred that the temperature of the drying is 60~100 DEG C, the dry time is 10~14 hours.
It is preferred that the acid is hydrochloric acid or sulfuric acid, preferably concentration is 1~3mol/L hydrochloric acid.
On the other hand, present invention also offers a kind of carbon fiber felt material of above-mentioned load stratiform manganese oxide in catalysis formaldehyde
In application.
Main advantages of the present invention are：
The present invention uses nitric acid pre-treatment carbon fiber felt carrier, then by the carbon fiber felt after liquor potassic permanganate and activation in acid
Property under the conditions of react, in-situ preparation is carried on the oxidation manganese material on carbon fiber mountain, this method have it is simple and easy to apply, it is environment-friendly,
With low cost the features such as.Catalyst mentioned by the present invention is a kind of carbon fibre material for having loaded δ phase oxidation manganese nanometer sheets, its
Middle manganese oxide nanometer sheet is layered crystal structure.Its layered crystal structure is beneficial to provide more avtive spots.And conduct
The active-carbon fibre material of matrix has loose structure, is conducive to absorbing formaldehyde gas.Stratiform has been loaded mentioned by the present invention
The carbon fibre material of manganese oxide has different surface oxygen species and certain low temperature reducibility, and this is all beneficial to urge
The progress of oxidation.
Brief description of the drawings
Fig. 1 is the FTIR collection of illustrative plates of the carbon fiber felt material before and after activation；
Fig. 2 is the different carbon fibre materials for having loaded stratiform manganese oxide and carbon fiber substrate material prepared by embodiment 1-3
XRD spectrum；
Fig. 3 is the SEM image and TEM image of the carbon fibre material for having loaded stratiform manganese oxide prepared by embodiment 1；
Fig. 4 is the SEM image and TEM image of the carbon fibre material for having loaded stratiform manganese oxide prepared by embodiment 2；
Fig. 5 is the SEM image and TEM image of the carbon fibre material for having loaded stratiform manganese oxide prepared by embodiment 3；
Fig. 6 is the H of the different carbon fibre materials for having loaded stratiform manganese oxide prepared by embodiment 1-32- TPR collection of illustrative plates；
Fig. 7 is the O of the different carbon fibre materials for having loaded stratiform manganese oxide prepared by embodiment 1-32- TPD collection of illustrative plates；
Fig. 8 is the NH of the different carbon fibre materials for having loaded stratiform manganese oxide prepared by embodiment 1-33- TPD collection of illustrative plates；
Fig. 9 is that the different carbon fibre materials for having loaded stratiform manganese oxide prepared by embodiment 1-3 are catalyzed when removing formaldehyde
Efficiency changes with time collection of illustrative plates.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The carbon fiber felt material for the load stratiform manganese oxide that the present invention is provided includes carbon fiber felt and growth in situ in institute
State the δ phase oxidation manganese nanometer sheets of carbon fiber surface in carbon fiber felt.Oxidation manganese material (δ phase oxidation manganese nanometer sheet) therein is knot
Brilliant good δ-MnO2.It is described load stratiform manganese oxide carbon fiber felt material have mesopore orbit, the diameter of mesopore orbit
Can be 14~19nm.The specific surface area of the carbon fiber felt material of the load stratiform manganese oxide is about 25.75~47.42m2/g。
Wherein δ-MnO2With layered crystal structure.In addition the carbon fiber felt material of the load stratiform manganese oxide also has necessarily low
Warm reproducibility and different surface oxygen species.δ phase oxidations manganese nanometer in the carbon fiber felt material of the load stratiform manganese oxide
The content of piece can be 21~24wt%.
The present invention uses strong oxidizing property low-kappa number carbon fiber felt, is then born on the carbon fiber felt after activation (pretreatment)
Carrier layer shape manganese oxide nanometer sheet.Illustrate to following exemplary the carbon fiber felt material for the load stratiform manganese oxide that the present invention is provided
Preparation method.
Carbon fiber felt is pre-processed using acid with strong oxidizing property.Specifically, carbon fiber felt is placed in acid with strong oxidizing property
In under 60-80 DEG C (such as 70 DEG C) heating water bath 3~5 hours, obtain pretreated carbon fiber felt.The acid with strong oxidizing property
Can be at least one of nitric acid, sulfuric acid, preferably concentration is 69% concentrated nitric acid.
Stratiform manganese oxide nanometer sheet (δ phase oxidation manganese nanometer sheet) is loaded on carbon fiber felt after activation.Specifically, will
Pretreated carbon fiber felt is impregnated in liquor potassic permanganate, and adding a certain amount of sour (such as hydrochloric acid, dilute sulfuric acid) makes Gao Meng
The pH of sour potassium solution to 1~2, then under 60-80 DEG C (preferably 60~70 DEG C, such as 65 DEG C) reaction (such as 6 is small within 3~9 hours
When) by washing, again dry at 60~100 DEG C, obtain the carbon fiber felt material of the load stratiform manganese oxide.Wherein carbon fiber
The mass ratio of felt and potassium permanganate can be (2~4)：10.The temperature of the drying can be 60~100 DEG C, and the dry time can be
10~14 hours.The concentration of the hydrochloric acid can be 1~3mol/L, such as 2mol/L.
In a preferred scheme, using salpeter solution activated carbon fiber, followed by liquor potassic permanganate and activated carbon
The active carbon fiber felt that redox reaction between fiber is prepared for loading sheet manganese oxide material under 65 DEG C of water-baths is urged
Agent.
In a preferred embodiment, (A) pre-processes carbon fiber felt using salpeter solution；(B) carbon after activation
Stratiform manganese oxide nanometer sheet is loaded on fibrofelt.In step (A), by 2.5g carbon fiber felts with a certain amount of concentration for 69% it is dense
Salpeter solution is handled 3-5 hours under conditions of 70 DEG C of water-baths, and then washing is dried to obtain the carbon fiber felt material of activation, is designated as
CF acid treatments.In step (B), at 65 DEG C, by 0.048gKMnO4It is dissolved in 100mL water, is stirred vigorously to after being completely dissolved and adds
Enter the carbon fiber felt material after activation, a certain amount of hydrochloric acid solution (2mol/L) is then added dropwise the pH value of solution is adjusted to 1-2, react
Washing is taken out after 6h and is dried in 80 DEG C of baking oven, the carbon fiber felt of load stratiform manganese oxide prepared by situ synthesis is obtained
Material.Wherein, step A) in nitric acid used can be other acid with strong oxidizing property.
Manganese oxide in the catalyst of the present invention is the δ phase oxidation manganese of well-crystallized, tool two-dimensional nano piece pattern and stratiform
Crystal structure, with higher specific surface area and meso-hole structure, certain low-temperature reduction and abundant surface oxygen species.When
During catalyst for removing low concentration formaldehyde, the catalytic efficiency of material PARA FORMALDEHYDE PRILLS(91,95) in 5h is 30% or so.The catalyst
Preparation method is simple and easy to apply, environmentally friendly, with low cost, it can also be used to which catalysis oxidation removes the catalysis of low concentration formaldehyde gas
Agent or VOC (VOC) gas.
The carbon fiber felt material of the load stratiform manganese oxide of the present invention is used for catalytic elimination low concentration formaldehyde as catalyst
Gas.Its catalytic performance characterize be by removing flow velocity for 52L/min, what concentration was estimated for 1ppm formaldehyde gas.
Experimentation is as follows：13g or so catalyst is cut into 25mm × 25mm square flaky material, is stacked up, is put into sample
Product are tested in storehouse.In whole course of reaction, sampled, and shown with ammonium ferric sulfate solution with phenol reagent every 0.5-1h
After colour response, content of formaldehyde is detected using ultraviolet spectrometer.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.The examination of unreceipted actual conditions in the following example
Proved recipe method, generally according to normal condition, or according to the condition proposed by manufacturer.Unless otherwise indicated, all percentage
With number by weight.If without specified otherwise, the carbon fiber felt used in following embodiments is commercially available finished product PAN carbon felts
(made using the former felt of polyacrylonitrile-radical flat board after pre-oxidation and carbonization treatment, obtain more convenient, application of being more convenient for.
Embodiment 1
2.5g carbon fiber felts are handled 3 hours with a certain amount of concentration for 69% concentrated nitric acid solution under conditions of 70 DEG C of water-baths,
Then washing is dried to obtain the carbon fiber felt material of activation, is designated as CF acid treatments., will at 65 DEG C in step (B)
0.048gKMnO4It is dissolved in 100mL water, is stirred vigorously to after being completely dissolved the carbon fiber felt material added after activation, then drips
Plus the pH value of solution is adjusted to and takes out washing after 2, reaction 6h and dried in 80 DEG C of baking oven by a certain amount of hydrochloric acid solution (2mol/L)
It is dry, the carbon fiber felt material of load stratiform manganese oxide prepared by situ synthesis is obtained, 3h-CF is designated as, wherein the load layer
The content of δ phase oxidations manganese nanometer sheet is 21.8wt% in the carbon fiber felt material of shape manganese oxide.
Embodiment 2
In order to examine differential responses pH value to remove the influence of formaldehyde performance to catalyst, by 2.5g carbon fiber felts with a certain amount of
Concentration is handled 3 hours for 69% concentrated nitric acid solution under conditions of 70 DEG C of water-baths, and then washing is dried to obtain the carbon fibre of activation
Felt material is tieed up, CF acid treatments are designated as.In step (B), at 65 DEG C, by 0.048gKMnO4It is dissolved in 100mL water, is stirred vigorously
The carbon fiber felt material added to after being completely dissolved after activation, is then added dropwise a certain amount of hydrochloric acid solution (2mol/L) by the pH of solution
Value, which is adjusted to, to be taken out washing after 1, reaction 6h and is dried in 80 DEG C of baking oven, obtains load stratiform oxidation prepared by situ synthesis
The carbon fiber felt material of manganese, is designated as 3h-CF-pH1, wherein δ phase oxidations in the carbon fiber felt material of the load layer shape manganese oxide
The content of manganese nanometer sheet is 23.1wt%.
Embodiment 3
In order to examine the different nitric acid pretreatment times to remove the influence of formaldehyde performance to catalyst, 2.5g carbon fiber felts are used
A certain amount of concentration is handled 5 hours for 69% concentrated nitric acid solution under conditions of 70 DEG C of water-baths, and then washing is dried to obtain activation
Carbon fiber felt material, be designated as CF acid treatments.In step (B), at 65 DEG C, by 0.048gKMnO4It is dissolved in 100mL water, it is acute
The carbon fiber felt material that strong stirring is added after activation to after being completely dissolved, a certain amount of hydrochloric acid solution (2mol/L) is then added dropwise will be molten
The pH value of liquid, which is adjusted to, to be taken out washing after 2, reaction 6h and is dried in 80 DEG C of baking oven, obtains load layer prepared by situ synthesis
The carbon fiber felt material of shape manganese oxide, is designated as 5h-CF, wherein δ phase oxygen in the carbon fiber felt material of the load layer shape manganese oxide
The content for changing manganese nanometer sheet is 22.6wt%.
Fig. 1 is the FTIR collection of illustrative plates of the carbon fiber felt material before and after activation.As seen from Figure 1, the work after nitric acid pretreatment
Property carbon fiber felt is in 1300~1600nm-1And 3400~3700nm-1There is obvious stretching vibration peak in place, and hydroxyl is corresponded to respectively
With carboxyl, this illustrates after being pre-processed into pernitric acid that carbon fiber surface occurs in that the active group of hydroxyl, carboxyl, and this is beneficial to
Carbon fiber reacts with potassium permanganate.
Fig. 2 is the XRD of the prepared different carbon fibre material for having loaded stratiform manganese oxide and carbon fiber substrate material
Collection of illustrative plates.From Figure 2 it can be seen that having loaded the δ-MnO of crystallization in carbon fiber substrate2(JCPDS 80-1098), wherein 2 θ=12.5 °,
25 °, 36.5 ° and 65.5 ° correspond respectively to (001), (002), (- 111) and (- 321) crystal face.Successfully born on this explanation carbon fiber
Oxidation manganese material is carried.
Fig. 3 is the SEM image and TEM image of the carbon fibre material for having loaded stratiform manganese oxide prepared by embodiment 1, figure
In 3 a and b are the SEM images of 3h-CF samples, it can be found that c in carbon fiber surface uniform load sheet oxidation manganese material, Fig. 3
It is the TEM image of 3h-CF samples, it can be found that the oxidation manganese material is sheet.Fig. 4 is the load prepared by embodiment 2
A and b is the SEM image of 3h-CF-pH1 samples in the SEM image and TEM image of the carbon fibre material of stratiform manganese oxide, Fig. 4, can
To find the rise (referring to that pH is increased to 1 by 2) with pH value in reaction, the oxidation manganese material of carbon fiber surface growth starts group
Poly-, c is the TEM image of 3h-CF-pH1 samples in Fig. 4, it can be found that the oxidation manganese material is still sheet.A and b are in Fig. 5
It is the SEM image of 5h-CF samples, it can be found that it is constant in pH value, in the case of the nitric acid pre-treatment time is increased.Carbon fiber surface
The TEM image that c in a certain degree of corrosion, Fig. 5 is 5h-CF samples is received, it can be found that the oxidation manganese material is still lamella
Shape.
Fig. 6 is the H of the prepared different carbon fibre materials for having loaded stratiform manganese oxide2- TPR collection of illustrative plates.Can from Fig. 6
Know：Peak at low temperature corresponds to Mn4+To Mn3+Conversion, positioned at the peak correspondence carbon fiber surface activity oxygen-containing group of middle-temperature section
The reduction of group, the peak at high temperature corresponds to Mn3+To Mn2+Conversion.It can be seen that by the relative area at peak：With reaction
The rise reaction of pH value carries out more complete, and surface active groups are reduced；With the increase of nitric acid pretreatment time, surface is lived
Property group increase, do not react away completely.Therefore, having loaded the carbon fibre material of stratiform manganese oxide also has certain low temperature also
Originality.
Fig. 7 is the O of the prepared different carbon fibre materials for having loaded stratiform manganese oxide2- TPD collection of illustrative plates.Can from Fig. 7
Know：Peak at low temperature corresponds to Adsorbed oxygen species, positioned at the peak of middle-temperature section for carbon fiber surface activity oxy radical oxygen
Species, the peak at high temperature corresponds to Lattice Oxygen.Therefore, the carbon fibre material of stratiform manganese oxide has been loaded also with different
Surface oxygen species.
Fig. 8 is the NH of the prepared different carbon fibre materials for having loaded stratiform manganese oxide3- TPD collection of illustrative plates.From Fig. 8
Understand：The acid adsorption site of the peak correspondence catalyst of low-temperature zone, the 3h-CF-pH1 samples it can be seen from the relative area at peak
The acidic site on surface is less, more conducively the absorption of formaldehyde gas.
Table 1 is the mesoporous parameter of the carbon fiber felt material of load stratiform manganese oxide nanometer sheet prepared by embodiment 1-3：
Effect example
The removal experiment of formaldehyde is carried out in a dynamic condition.Gas flow rate is 52L/min, and concentration of formaldehyde is 1ppm.Experiment
Process is as follows：13g or so catalyst (carbon fibre material for having loaded stratiform manganese oxide prepared by embodiment 1-3) is cut into
25mm × 25mm square flaky material, is stacked up, and is put into sample bin and is tested, used catalyst consumption is total up to
10g.In whole course of reaction, sampled, and carried out with ammonium ferric sulfate solution after chromogenic reaction with phenol reagent every 0.5-1h, made
Content of formaldehyde is detected with ultraviolet spectrometer.The removal efficiency of formaldehyde is calculated according to below equation and obtained：Removal efficiency=
(CEntrance-COutlet)/CEntrance。
Fig. 9 catalytic efficiencies that are the prepared different carbon fibre materials for having loaded stratiform manganese oxide when removing formaldehyde with
The change collection of illustrative plates of time.The carbon fiber felt material for having loaded manganese oxide prepared by embodiment 1 and embodiment 3 is in 5h to concentration
For 1ppm formaldehyde gas catalytic efficiency all below 30%.The carbon fiber felt for having loaded manganese oxide prepared by embodiment 2
Material is of a relatively high for the catalytic efficiency of 1ppm formaldehyde gas to concentration in 5h, 30% or so.
All documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. a kind of carbon fiber felt material for loading stratiform manganese oxide, it is characterised in that including carbon fiber felt and growth in situ in
The δ phase oxidation manganese nanometer sheets of carbon fiber surface in the carbon fiber felt, the δ phase oxidations manganese nanometer sheet has layered crystal knot
Structure.
2. the carbon fiber felt material of stratiform manganese oxide is loaded according to claim 1, it is characterised in that the load stratiform oxygen
The content for changing δ phase oxidation manganese nanometer sheets in the carbon fiber felt material of manganese is 21~24wt%.
3. the carbon fiber felt material of load stratiform manganese oxide according to claim 1 or claim 2, it is characterised in that the load layer
The specific surface area of the carbon fiber felt material of shape manganese oxide is 25.75~47.42 m2/ g, mesopore orbit a diameter of 14~19nm.
4. a kind of preparation method for the carbon fiber felt material that stratiform manganese oxide is loaded as any one of claim 1-3, its
It is characterised by, including：
Carbon fiber felt is pre-processed using acid with strong oxidizing property；
Pretreated carbon fiber felt is impregnated in liquor potassic permanganate, adding a certain amount of acid makes the pH of liquor potassic permanganate extremely
1~2, through washing, drying after then being reacted 3~9 hours at 60~80 DEG C, the carbon for obtaining the load stratiform manganese oxide is fine
Tie up felt material.
5. preparation method according to claim 4, it is characterised in that carbon fiber felt is placed in acid with strong oxidizing property 60~
Heating water bath 3~5 hours at 80 DEG C, obtain pretreated carbon fiber felt.
6. the preparation method according to claim 4 or 5, it is characterised in that the acid with strong oxidizing property is selected from nitric acid or/and sulphur
Acid, preferably concentration are 69% concentrated nitric acid.
7. the preparation method according to any one of claim 4-6, it is characterised in that the matter of carbon fiber felt and potassium permanganate
Measuring ratio is（2~4）：10.
8. the preparation method according to any one of claim 4-7, it is characterised in that the temperature of the drying is 60~
100 DEG C, the dry time is 10~14 hours.
9. the preparation method according to any one of claim 4-8, it is characterised in that the acid is hydrochloric acid or sulfuric acid, excellent
Concentration is elected as 1~3 mol/L hydrochloric acid.
10. a kind of carbon fiber felt material that stratiform manganese oxide is loaded as any one of claim 1-3 is in catalysis formaldehyde
Application.
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| CN108176412A (en) * | 2018-01-26 | 2018-06-19 | 华南理工大学 | A kind of fiber/nano-manganese dioxide composite material and preparation method and application |
| CN108816244A (en) * | 2018-05-30 | 2018-11-16 | 华南理工大学 | A kind of nano carbon-base composite material and preparation method of catalyzing oxidizing degrading formaldehyde and application |
| CN109546163A (en) * | 2018-11-15 | 2019-03-29 | 电子科技大学 | A kind of method of modifying of organic flow battery graphite felt electrode |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108176412A (en) * | 2018-01-26 | 2018-06-19 | 华南理工大学 | A kind of fiber/nano-manganese dioxide composite material and preparation method and application |
| CN108176412B (en) * | 2018-01-26 | 2021-03-30 | 华南理工大学 | Fiber/nano manganese dioxide composite material, preparation method and application |
| CN108816244A (en) * | 2018-05-30 | 2018-11-16 | 华南理工大学 | A kind of nano carbon-base composite material and preparation method of catalyzing oxidizing degrading formaldehyde and application |
| CN108816244B (en) * | 2018-05-30 | 2020-12-22 | 华南理工大学 | Nano carbon-based composite material for catalytic oxidation degradation of formaldehyde and preparation method and application thereof |
| CN109546163A (en) * | 2018-11-15 | 2019-03-29 | 电子科技大学 | A kind of method of modifying of organic flow battery graphite felt electrode |
| CN109546163B (en) * | 2018-11-15 | 2021-09-24 | 电子科技大学 | Modification method of graphite felt electrode for organic flow battery |
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