CN108554402A - Manganese dioxide/carbon cloth composite material and preparation method and application and air cleaning unit - Google Patents
Manganese dioxide/carbon cloth composite material and preparation method and application and air cleaning unit Download PDFInfo
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- CN108554402A CN108554402A CN201810298666.8A CN201810298666A CN108554402A CN 108554402 A CN108554402 A CN 108554402A CN 201810298666 A CN201810298666 A CN 201810298666A CN 108554402 A CN108554402 A CN 108554402A
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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
- B01J23/16—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
A kind of preparation method of manganese dioxide/carbon cloth composite material, including：Carbon cloth and permanganate solution, a concentration of 10mmol/L to 300mmol/L of the permanganate solution are provided；And the carbon cloth is placed in the permanganate solution .5h to 48h is set to 0 in 0 DEG C to 80 DEG C of temperature condition decentralization, obtains the manganese dioxide/carbon cloth composite material.The present invention also provides a kind of manganese dioxide/carbon cloth composite material and its application and a kind of air cleaning units.
Description
Technical field
The present invention relates to air purification fields, more particularly to a kind of manganese dioxide/carbon cloth composite material and its preparation side
Method and application and air cleaning unit.
Background technology
Formaldehyde in indoor air level of pollution directly influences the health of long-term people movable indoors, for first
The features such as aldehyde has concentration low, and deenergized period is long, people have done a large amount of research work to how to remove indoor formaldehyde.According to correlation
The time of report, people waited in environment indoors in life is more than 80% or more, improves indoor air quality, studies and efficiently goes first
The method of aldehyde has become the research hotspot in room air field.
Catalytic oxidation technologies are a kind of methods of effective removal formaldehyde, however, current catalytic oxidation technologies are mainly
Accelerate the oxidative degradation of formaldehyde at room temperature using catalyst such as Mn oxides, the degradation rate of PARA FORMALDEHYDE PRILLS(91,95) is slow, and conversion ratio is low, drop
The effect for solving formaldehyde is less desirable.
Invention content
Based on this, it is necessary to provide a kind of manganese dioxide/carbon cloth composite material that capableing of efficient degradation formaldehyde and its preparation
Methods and applications.
A kind of preparation method of manganese dioxide/carbon cloth composite material, including：Carbon cloth and permanganate solution, institute are provided
State a concentration of 10mmol/L to 300mmol/L of permanganate solution；And the carbon cloth is placed in the permanganate solution
In .5h to 48h is set to 0 in 0 DEG C to 80 DEG C of temperature condition decentralization, obtains the manganese dioxide/carbon cloth composite material.
A concentration of 40mmol/L to 200mmol/L of the permanganate solution in one of the embodiments,.
Standing time of the carbon cloth in the permanganate solution is 5h to 15h in one of the embodiments,.
The reaction temperature of the carbon cloth and the permanganate solution is 20 DEG C to 60 DEG C in one of the embodiments,.
In one of the embodiments, the carbon cloth before being positioned over the permanganate solution without chemistry or high temperature
Activation process.
The permanganate solution is made of permanganate and water in one of the embodiments,.
The permanganate in the permanganate solution is potassium permanganate, sodium permanganate, height in one of the embodiments,
At least one of calcium manganate, high manganese lithium, barium permanganate, zinc permanganate and magnesium permanganate.
A kind of manganese dioxide/carbon cloth composite material, including carbon cloth and MnO2Nanoscale twins, the MnO2Nanoscale twins coat
In the carbon fiber surface of the carbon cloth, the MnO2Nanoscale twins include multiple MnO2Nanometer sheet.
The load capacity of manganese dioxide is in the manganese dioxide/carbon cloth composite material in one of the embodiments,
0.1wt% to 10wt%.
The load capacity of manganese dioxide is in the manganese dioxide/carbon cloth composite material in one of the embodiments,
0.5wt% to 6wt%.
The sheet resistance of the manganese dioxide/carbon cloth composite material is 2 Ω to 50 Ω in one of the embodiments,.
The MnO in one of the embodiments,2The thickness of nanoscale twins is 60nm to 1 μm.
The MnO in one of the embodiments,2Nanometer sheet is δ-MnO2Nanometer sheet.
The chemical valence form of manganese element includes in the manganese dioxide/carbon cloth composite material in one of the embodiments,
Manganic and tetravalent manganese, and the average valence of the manganese element is 3.4~3.9.
The manganese dioxide/carbon cloth composite material is obtained by above-mentioned preparation method in one of the embodiments,.
A kind of application of the manganese dioxide/carbon cloth composite material in removing formaldehyde.
In one of the embodiments, first is removed by applying voltage on the manganese dioxide/carbon cloth composite material
Aldehyde.
A kind of air cleaning unit, including the manganese dioxide/carbon cloth composite material and voltage application device, the voltage
Bringing device and manganese dioxide/carbon cloth composite material electrical connection, for being applied on the manganese dioxide/carbon cloth composite material
Add a voltage.
The voltage application device includes two electrodes in one of the embodiments, and described two electrodes are respectively set
In the both ends of the manganese dioxide/carbon cloth composite material, described two electrodes are for being electrically connected to a power source.
The present invention by carried out on carbon cloth reaction in-situ to by manganese dioxide load on the carbon cloth, described in formation
Manganese dioxide/carbon cloth composite material, wherein efficient thermal transfer interface, institute are formed between manganese dioxide and the carbon fiber of carbon cloth
State heat that manganese dioxide/carbon cloth composite material generates in the energized state can fast transfer to manganese dioxide, so as to efficient
Ground is catalyzed Degradation Formaldehyde.
In addition, the available manganese dioxide/carbon cloth for having both good thermoelectricity capability, mechanical performance and catalytic performance of the present invention is multiple
Condensation material, the manganese dioxide/carbon cloth composite material can repeatedly, repeatedly carry out energization use, will not be broken, fall
Phenomena such as slag, broken hole, and PARA FORMALDEHYDE PRILLS(91,95) have higher degradation efficiency and conversion ratio, can large-scale application gone in indoor formaldehyde
It removes.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates for the manganese dioxide/carbon cloth composite material that the embodiment of the present invention 1 provides；
Fig. 2 e and Fig. 2 f are respectively C element and Mn members in the manganese dioxide/carbon cloth composite material that the embodiment of the present invention 1 provides
The X-ray energy dispersion Elemental redistribution (EDX mapping) of element, Fig. 2 g are the manganese dioxide/carbon cloth that the embodiment of the present invention 1 provides
Field emission scanning electron microscope (SEM) photo of the cross section of composite material；
Fig. 3 is the Flied emission scanning electron microscopy for the manganese dioxide/carbon cloth composite material surface that the embodiment of the present invention 1 provides
Mirror (SEM) photo；
Fig. 4 is the transmission electron microscope for the manganese dioxide/carbon cloth composite material surface that the embodiment of the present invention 1 provides
(TEM) photo；
Fig. 5 is the manganese dioxide/carbon cloth composite material that provides of the embodiment of the present invention 1 concentration of formaldehyde in Degradation Formaldehyde experiment
With gas concentration lwevel time history plot；
Fig. 6 is the repeat performance figure for the manganese dioxide/carbon cloth composite material that the embodiment of the present invention 1 provides.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, by the following examples, it and combines attached
Figure, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining this hair
It is bright, it is not intended to limit the present invention.
First embodiment of the invention provides a kind of preparation method of manganese dioxide/carbon cloth composite material, including：
S1 provides carbon cloth and permanganate solution, the concentration 10mmol/L to 300mmol/ of the permanganate solution
L；And
The carbon cloth is placed in the permanganate solution by S2, and 0.5h~48h is placed under conditions of 0 DEG C~80 DEG C,
Obtain the manganese dioxide/carbon cloth composite material.
The embodiment of the present invention by carried out on carbon cloth reaction in-situ to by manganese dioxide load on the carbon cloth, shape
At the manganese dioxide/carbon cloth composite material, wherein form efficient heat transfer circle between manganese dioxide and the carbon fiber of carbon cloth
Face, the heat that the manganese dioxide/carbon cloth composite material generates in the energized state can fast transfer to manganese dioxide, so as to
Efficiently it is catalyzed Degradation Formaldehyde.
In step sl, the carbon cloth refers to carbon fiber preform rather than this kind of non-woven fabrics of carbon fiber felt, i.e., the described carbon
Cloth is woven by more carbon fibers and forms conductive network structure.Preferably, the carbon cloth has good flexibility, and has
Certain intensity, so that the manganese dioxide/carbon cloth composite material that step S2 is obtained also has certain flexibility and intensity,
Make its using and moving process in not easy to break, fragmentation and scaling-off, and can easily be powered, so as to repeatedly, it is more
It uses secondaryly.
The permanganate solution may include permanganate and solvent.The permanganate may include potassium permanganate, Gao Meng
At least one of sour sodium, acerdol, high manganese lithium, barium permanganate, zinc permanganate and magnesium permanganate, the solvent can be
Water.Preferably, do not include that can be chemically reacted with the carbon cloth in addition to the permanganate in the permanganate solution
Ingredient, to prevent other compositions from influencing the mechanical performance of the manganese dioxide/carbon cloth composite material.It is further preferable that described
Permanganate solution is made of the permanganate and water.
In step s 2, when the carbon cloth is infiltrated on the permanganate solution, MnO4 -Ionic adsorption is in the carbon of carbon cloth
Fiber surface simultaneously obtains electronics to be reduced to MnO from carbon atom2, the MnO that restores2In the carbon fiber surface knot
Crystals growth obtains multiple MnO2Nanometer sheet, the multiple MnO2Nanometer sheet is interconnected to form multiple ducts, more to obtain having
The MnO of pore structure2Nanoscale twins.The MnO2The porous structure of nanoscale twins is conducive to formaldehyde adsorption and is capable of providing more
Catalysis reaction site, so as to make the manganese dioxide/carbon cloth composite material have higher catalytic activity；In addition, described
MnO2Nanometer sheet and the surface of the carbon fiber are bound tightly together, and form efficient thermal transfer interface, when to described two
When manganese oxide/carbon cloth composite material applies voltage, heat is generated due to the pyroelectric effect of the carbon cloth, and be transferred quickly to two
Manganese oxide, to make the manganese dioxide that can efficiently be catalyzed Degradation Formaldehyde.
The load capacity of manganese dioxide is bigger on the carbon cloth, and the conversion ratio of PARA FORMALDEHYDE PRILLS(91,95) is higher, however, with the titanium dioxide
The resistance of the increase of manganese load capacity, the carbon cloth can become larger, and thermoelectricity capability and flexibility can reduce, and on the one hand can make the dioxy
Change manganese/carbon cloth composite material to be easily broken off, on the other hand, the manganese dioxide/carbon cloth composite material can be reduced in energized state
The catalytic efficiency of lower PARA FORMALDEHYDE PRILLS(91,95).Preferably, the load capacity of manganese dioxide in the manganese dioxide/carbon cloth composite material can be controlled
In 0.1wt% between 10wt%, may make the manganese dioxide/carbon cloth composite material there is preferable machinery in the range
Performance, phenomena such as fracture, scaling-off, broken hole will not occur.It is further preferable that the load capacity of the manganese dioxide be 0.5wt% extremely
6wt% can make the formaldehyde have preferable pyroelectric effect, so as to make the manganese dioxide/carbon cloth composite wood in the range
Not only PARA FORMALDEHYDE PRILLS(91,95) has higher conversion ratio to material, but also has higher degradation rate.It is further preferable that the manganese dioxide/
The load capacity of manganese dioxide is 1wt% to 5wt% in carbon cloth composite material.
The concentration of the permanganate solution is controlled in 10mmol/L between 300mmol/L, reaction temperature is controlled
It between 0 DEG C~80 DEG C, will control between 0.5h~48h in the reaction time, the load capacity that can get manganese dioxide is 0.1wt%
To the manganese dioxide/carbon cloth composite material of 10wt%.Preferably, a concentration of 40mmol/L of the permanganate solution is extremely
200mmol/L.It is highly preferred that a concentration of 90mmol/L of the permanganate solution is between 150mmol/L.Preferably, institute
It is 20 DEG C to 60 DEG C to state reaction temperature.Preferably, the reaction time is 0.5h~for 24 hours, it is further preferable that the reaction time
For 5h~15h.
Preferably, the carbon cloth before being placed in the permanganate solution without other chemical treatment or high-temperature activation
Processing, to prevent carbon cloth mechanical degradation after the chemical treatment, to cannot obtain having good flexibility and
The manganese dioxide/carbon cloth composite material of intensity.Here chemical treatment is to instigate the changed processing of the chemical composition of carbon cloth
Step, such as pickling.Here high-temperature activation refers to that carbon cloth is carried out to high-temperature process (such as 500 under the protection of inert gas
DEG C or more), to carry out pore-creating to carbon cloth.Preferably, the carbon cloth can be placed directly in the permanganate solution, or only be passed through
Cross washing, alcohol is washed is placed in the permanganate solution.
It, can be by the manganese dioxide/carbon cloth composite material from the height after obtaining the manganese dioxide/carbon cloth composite material
The molten middle taking-up of manganate, and further washed, be dried.It can be used deionized water multiple to the manganese dioxide/carbon cloth
Condensation material is washed.The manganese dioxide/carbon cloth composite material can be dried under conditions of less than 200 DEG C.
Second embodiment of the invention provides a kind of manganese dioxide/carbon cloth composite material, including carbon cloth and MnO2Nanometer sheet
Layer, the MnO2Nanoscale twins are coated on the carbon fiber surface of the carbon cloth, the MnO2Nanoscale twins include multiple MnO2Nanometer
Piece, the multiple MnO2Nanometer sheet is interconnected to form multiple ducts.The MnO2The porous structure of nanoscale twins is conducive to adsorb
Formaldehyde and more catalysis reaction sites are capable of providing, it is higher so as to make the manganese dioxide/carbon cloth composite material have
Catalytic activity, the MnO2Efficient thermal transfer interface is formed between nanometer sheet and the carbon fiber, when the manganese dioxide/
When carbon cloth composite material is powered, the carbon cloth can generate more heats, and be quickly transmitted to the MnO2Nanometer sheet, from
And make MnO2Nanometer sheet being capable of fast and efficiently degradation of formaldehyde.
The load capacity of manganese dioxide can be 0.1wt% to 10wt% in the manganese dioxide/carbon cloth composite material, preferably
0.5wt% to 6wt%, more preferably 1wt% are to 5wt%.The MnO2The thickness of nanoscale twins can be 60nm to 1 μm, more excellent
It is selected as 60nm to 200nm, may be, for example, 120nm.The MnO2Nanometer sheet can be δ-MnO2Nanometer sheet.The manganese dioxide/carbon cloth
The sheet resistance of composite material can be 2 Ω to 50 Ω, more preferably 5 Ω to 30 Ω.In the manganese dioxide/carbon cloth composite material
The chemical valence form of manganese element includes manganic and tetravalent manganese, and the average valence of the manganese element is 3.4~3.9, more preferably
It is 3.4~3.6, Mn in the manganese dioxide/carbon cloth composite material3+/Mn4+Ratio it is higher, illustrate the manganese dioxide of load
Crystal defect is more, so as to adsorb more oxygen species, is more advantageous to the catalytic degradation of formaldehyde.
The preparation method that the manganese dioxide/carbon cloth composite material can be provided by first embodiment of the invention is prepared into
It arrives.
Third embodiment of the invention provides a kind of manganese dioxide/carbon cloth composite material answering in removing formaldehyde
With.Preferably, when removing formaldehyde, a voltage can be applied on the manganese dioxide/carbon cloth composite material.In an embodiment
In, an electrode can be respectively set at the opposite both ends of the manganese dioxide/carbon cloth composite material, by the electrode to described two
Manganese oxide/carbon cloth composite material applies voltage.It should be appreciated that can not also be to the manganese dioxide/carbon cloth composite material
Apply voltage, and is placed directly in interior and removes formaldehyde at room temperature.
Four embodiment of the invention provides a kind of air cleaning unit, and the air cleaning unit includes the titanium dioxide
Manganese/carbon cloth composite material and voltage application device, the voltage application device and the manganese dioxide/carbon cloth composite material are electrically connected
It connects, for applying voltage to manganese dioxide/carbon cloth composite material.The voltage application device may include two electrodes, described two
A electrode may be disposed at the both ends of the manganese dioxide/carbon cloth composite material, and be electrically connected to a power source.
Embodiment 1
Take 1mg potassium permanganate (KMnO4) be dissolved in 70mL deionized waters and form KMnO4Then one block size is by solution
The carbon cloth (being denoted as CC) of 4cm × 4cm immerses the KMnO4In solution, and reaction temperature is maintained at 60 DEG C and stands 5 hours,
Finally carbon cloth is taken out, is washed with deionized and dry at 105 DEG C, the manganese dioxide/carbon cloth composite material, note is made
For MnO2-CC.The manganese dioxide/carbon cloth composite material is observed, finds the manganese dioxide/carbon cloth composite material completely without broken
Damage, arbitrarily distorts the manganese dioxide/carbon cloth composite material, and no fracture, slag-off phenomenon occur.
To CC and MnO2- CC carries out Degradation Formaldehyde experiment：
In MnO2Copper electrode is respectively set in both ends opposite-CC, by MnO2- CC is placed at the stainless steels of 800mL at 25 DEG C
In reactor, 30min is placed in the case that cold, then by the copper electrode to MnO2- CC applies voltage, passes through light
Sound field gas monitor (INNOVA AirTech Instruments, Model 1412) on-line checking HCHO and carbon dioxide
Real-time concentration.
Embodiment 2
Take 0.5mg potassium permanganate (KMnO4) be dissolved in 70mL deionized waters and form KMnO4Then one block size is by solution
The carbon cloth of 4cm × 4cm immerses the KMnO4In solution, and reaction temperature is maintained at 60 DEG C and stands 5 hours, finally by carbon
Cloth takes out, and is washed with deionized and dry at 105 DEG C, the manganese dioxide/carbon cloth composite material is made.Observe described two
Manganese oxide/carbon cloth composite material finds the manganese dioxide/carbon cloth composite material intact unbroken, to the manganese dioxide/carbon
Cloth composite material is arbitrarily distorted, and no fracture, slag-off phenomenon occur.
Degradation Formaldehyde experiment is carried out using method same as Example 1.
Embodiment 3
Take 1.5mg potassium permanganate (KMnO4) be dissolved in 70mL deionized waters and form KMnO4Then one block size is by solution
The carbon cloth of 4cm × 4cm immerses the KMnO4In solution, and reaction temperature is maintained at 60 DEG C and stands 5 hours, finally by carbon
Cloth takes out, and is washed with deionized and dry at 105 DEG C, the manganese dioxide/carbon cloth composite material is made.Observe described two
Manganese oxide/carbon cloth composite material finds the manganese dioxide/carbon cloth composite material intact unbroken, to the manganese dioxide/carbon
Cloth composite material is arbitrarily distorted, and no fracture, slag-off phenomenon occur.
Degradation Formaldehyde experiment is carried out using method same as Example 1.
Embodiment 4
Take 1mg potassium permanganate (KMnO4) be dissolved in 70mL deionized waters and form KMnO4Then one block size is by solution
The carbon cloth of 4cm × 4cm immerses the KMnO4In solution, and reaction temperature is maintained at 60 DEG C and stands 1 hour, finally by carbon
Cloth takes out, and is washed with deionized and dry at 105 DEG C, the manganese dioxide/carbon cloth composite material is made.Observe described two
Manganese oxide/carbon cloth composite material finds the manganese dioxide/carbon cloth composite material intact unbroken, to the manganese dioxide/carbon
Cloth composite material is arbitrarily distorted, and no fracture, slag-off phenomenon occur.
Degradation Formaldehyde experiment is carried out using method same as Example 1.
Embodiment 5
Take 1mg potassium permanganate (KMnO4) be dissolved in 70mL deionized waters and form KMnO4Then one block size is by solution
The carbon cloth of 4cm × 4cm immerses the KMnO4In solution, and reaction temperature is maintained at 60 DEG C and stands 15 hours, finally by carbon
Cloth takes out, and is washed with deionized and dry at 105 DEG C, the manganese dioxide/carbon cloth composite material is made.Observe described two
Manganese oxide/carbon cloth composite material finds the manganese dioxide/carbon cloth composite material intact unbroken, to the manganese dioxide/carbon
Cloth composite material is arbitrarily distorted, and no fracture, slag-off phenomenon occur.
Degradation Formaldehyde experiment is carried out using method same as Example 1.
Comparative example 1
Take 4mg potassium permanganate (KMnO4) be dissolved in 70mL deionized waters and form KMnO4Then one block size is by solution
The carbon cloth of 4cm × 4cm immerses the KMnO4In solution, and reaction temperature is maintained at 60 DEG C and stands 5 hours, finally by carbon
Cloth takes out, and is washed with deionized and dry at 105 DEG C, the manganese dioxide/carbon cloth composite material is made.Observe described two
Manganese oxide/carbon cloth composite material finds that broken hole phenomenon occurs in the manganese dioxide/carbon cloth composite material, to the manganese dioxide/
Carbon cloth composite material is distorted, and slag-off phenomenon occurs.
Comparative example 2
CC samples use by embodiment 1 and MnO2The identical methods of-CC carry out Degradation Formaldehyde experiment.
The resistance data and Degradation Formaldehyde of 2 manganese dioxide/carbon cloth composite material of 1 1~embodiment of embodiment 5 of table and comparative example
Data in experiment when making alive reacts 20s
It is observed from fig. 1 that positioned at 12.3 °, 24.6 °, 36.5 ° and 66.5 ° of four characteristic diffraction peaks, correspond to stratiform two
Manganese oxide shows that manganese dioxide successfully loads on carbon cloth.A large amount of distortions are can see from Fig. 2 g and porous nanometer sheet is mutual
It is linked, forms the nanoscale twins for being evenly distributed on the thickness about 120nm on carbon fiber surface, formed between the nanometer sheet more
A duct.Can be seen that from Fig. 2 e and Fig. 2 f has close interface between Mn elements and C element, illustrate carbon fiber and MnO2
Efficient thermal transfer interface is formd between nanometer sheet.As seen from Figure 3, nanoscale twins are evenly coated at carbon fiber surface.From
The parallel stripes of Fig. 4 nanoscale twins edge show that nanoscale twins are made of a small number of stack layers, further demonstrate nanoscale twins
Porous structure.
From fig. 5, it can be seen that in the case of no application voltage, concentration of formaldehyde declines quickly, and gas concentration lwevel is but
It does not increase considerably correspondingly, i.e., is not converted into carbon dioxide in this stage formaldehyde, however, when applying 4V~8V's
When voltage, gas concentration lwevel start quickly, be dramatically increased, in addition, the manganese dioxide/carbon cloth composite material surface
Temperature reaches 58.6 DEG C under 4V voltages, and 85.8 DEG C are reached under 6V voltages, and 123.8 DEG C are reached under 8V voltages, is thus illustrated
The manganese dioxide/carbon cloth composite material has pyroelectric effect, and the pyroelectric effect can accelerate the Degradation and Transformation rate of formaldehyde.
From fig. 6, it can be seen that the manganese dioxide/carbon cloth composite material is by being used for multiple times, PARA FORMALDEHYDE PRILLS(91,95) still keeps higher, steadily goes
Except rate.
The present invention can get the manganese dioxide/carbon cloth composite wood for having both good thermoelectricity capability, mechanical performance and catalytic performance
Material, the manganese dioxide/carbon cloth composite material can repeatedly, repeatedly carry out energization use, will not occur fracture, it is scaling-off, broken
Phenomena such as hole, and PARA FORMALDEHYDE PRILLS(91,95) have higher degradation efficiency and conversion ratio, can large-scale application in the removal of indoor formaldehyde.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (19)
1. a kind of preparation method of manganese dioxide/carbon cloth composite material, including：
Carbon cloth and permanganate solution, a concentration of 10mmol/L to 300mmol/L of the permanganate solution are provided；And
The carbon cloth is placed in the permanganate solution .5h to 48h is set to 0 in 0 DEG C to 80 DEG C of temperature condition decentralization, obtains
To the manganese dioxide/carbon cloth composite material.
2. the preparation method of manganese dioxide/carbon cloth composite material according to claim 1, which is characterized in that the Gao Meng
A concentration of 40mmol/L to 200mmol/L of acid salt solution.
3. the preparation method of manganese dioxide/carbon cloth composite material according to claim 2, which is characterized in that the carbon cloth
Standing time in the permanganate solution is 5h to 15h.
4. the preparation method of manganese dioxide/carbon cloth composite material according to claim 2, which is characterized in that the carbon cloth
Reaction temperature with the permanganate solution is 20 DEG C to 60 DEG C.
5. the preparation method of manganese dioxide/carbon cloth composite material according to claim 1, which is characterized in that the carbon cloth
It is handled without chemistry or high-temperature activation before being positioned over the permanganate solution.
6. the preparation method of manganese dioxide/carbon cloth composite material according to claim 1, which is characterized in that the Gao Meng
Acid salt solution is made of permanganate and water.
7. the preparation method of manganese dioxide/carbon cloth composite material according to claim 1, which is characterized in that the Gao Meng
Permanganate in acid salt solution be potassium permanganate, sodium permanganate, acerdol, high manganese lithium, barium permanganate, zinc permanganate and
At least one of magnesium permanganate.
8. a kind of manganese dioxide/carbon cloth composite material, including carbon cloth and MnO2Nanoscale twins, the MnO2Nanoscale twins are coated on
The carbon fiber surface of the carbon cloth, the MnO2Nanoscale twins include multiple MnO2Nanometer sheet.
9. manganese dioxide/carbon cloth composite material according to claim 8, which is characterized in that the manganese dioxide/carbon cloth is multiple
The load capacity of manganese dioxide is 0.1wt% to 10wt% in condensation material.
10. manganese dioxide/carbon cloth composite material according to claim 9, which is characterized in that the manganese dioxide/carbon cloth
The load capacity of manganese dioxide is 0.5wt% to 6wt% in composite material.
11. manganese dioxide/carbon cloth composite material according to claim 8, which is characterized in that the manganese dioxide/carbon cloth
The sheet resistance of composite material is 2 Ω to 50 Ω.
12. manganese dioxide/carbon cloth composite material according to claim 8, which is characterized in that the MnO2Nanoscale twins
Thickness is 60nm to 1 μm.
13. manganese dioxide/carbon cloth composite material according to claim 8, which is characterized in that the MnO2Nanometer sheet is δ-
MnO2Nanometer sheet.
14. manganese dioxide/carbon cloth composite material according to claim 8, which is characterized in that the manganese dioxide/carbon cloth
The chemical valence form of manganese element includes manganic and tetravalent manganese in composite material, and the average valence of the manganese element be 3.4~
3.9。
15. manganese dioxide/carbon cloth composite material according to claim 8, which is characterized in that any by claim 1 to 6
The preparation method of manganese dioxide/carbon cloth composite material described in obtains.
16. a kind of such as claim 8 to 15 any one of them manganese dioxide/carbon cloth composite material answering in removing formaldehyde
With.
17. the application of manganese dioxide/carbon cloth composite material according to claim 16, which is characterized in that by described
Apply voltage on manganese dioxide/carbon cloth composite material to remove formaldehyde.
18. a kind of air cleaning unit, including such as claim 8 to 15 any one of them manganese dioxide/carbon cloth composite material
And voltage application device, the voltage application device and manganese dioxide/carbon cloth composite material electrical connection, for described two
Apply a voltage on manganese oxide/carbon cloth composite material.
19. air cleaning unit according to claim 18, which is characterized in that the voltage application device includes two electricity
Pole, described two electrodes are respectively arranged at the both ends of the manganese dioxide/carbon cloth composite material, and described two electrodes are used for and electricity
Source is electrically connected.
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