CN108176412B - Fiber/nano manganese dioxide composite material, preparation method and application - Google Patents
Fiber/nano manganese dioxide composite material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a fiber/nano manganese dioxide composite material and a preparation method and application thereof, and the preparation method comprises the following steps: (1) pretreating the fiber raw material: carrying out selective oxidation treatment on the fiber raw material, and washing the fiber raw material to be neutral to obtain oxidized fiber; (2) preparing a composite material: washing the oxidized fiber to neutrality after diluted acid treatment, and reacting with Mn2+And uniformly mixing and stirring the solution, adding an oxidant for reaction, washing and drying to finally obtain the in-situ grown nano manganese dioxide fiber. The nano manganese dioxide particles obtained by the method have narrow particle size distribution, are uniformly distributed on the surface of the fiber and are not easy to fall off, the obtained product has the excellent performances of the fiber and the nano manganese dioxide, can be processed into a wood functional material with both decoration and functionality, can be used for catalytically purifying formaldehyde in a non-illumination room, and enriches the application field of the nano manganese dioxide.
Description
Technical Field
The invention belongs to the field of organic and inorganic composite materials, and relates to a method for in-situ growth of nano manganese dioxide on fibers, wherein the obtained fiber/nano manganese dioxide composite material is used for catalytic purification of formaldehyde.
Background
Formaldehyde is a colorless gas, has strong pungent odor and high toxicity, can cause great harm to the olfactory sensation, lung, liver and immune functions of human bodies, can also combine with amino groups in proteins to generate cell mutation, and is defined as a substance with carcinogenicity and teratogenicity by the world health organization. The formaldehyde in the room is mainly from the artificial products such as decorative materials, plywood, fiber boards, particle boards and the like, and the artificial products mostly use urea formaldehyde resin as a binder and are subjected to preservative treatment by using formaldehyde, so that free formaldehyde is often released into the air in the room during use. With the popularization of environmental protection knowledge, more and more people are aware of the importance and urgency of purifying indoor air. The existing methods for purifying indoor formaldehyde mainly comprise a physical adsorption method, a photocatalytic oxidation method and a heterogeneous catalytic oxidation method. The adsorption method mainly uses activated carbon, but only transfers formaldehyde in the air to the adsorbent, and does not eliminate the formaldehyde, and the adsorbent is difficult to regenerate, water vapor in the air has great influence on the adsorption quantity of the formaldehyde, the photocatalytic oxidation method can only be carried out under the condition of illumination, and the heterogeneous catalytic oxidation method is always the key point in the research of removing the formaldehyde due to the advantages of high catalytic efficiency, no additional condition when in use and the like.
Manganese dioxide (MnO)2) The manganese dioxide is a common solid heterogeneous catalytic oxidation material, is often used for catalytic degradation of organic compounds, and is particularly used for degradation of volatile organic compounds, wherein the reaction of catalytic oxidative decomposition of formaldehyde by manganese dioxide is as follows: HCOH + O2→CO2+H2And O. The method for removing formaldehyde by using manganese dioxide at room temperature has the advantages of simple and convenient operation, low energy consumption, mild reaction conditions and the like, can degrade formaldehyde into water and carbon dioxide at normal temperature and normal pressure, does not generate secondary pollutants such as CO, HCOOH and the like, has good removal effect, and does not need illumination compared with a photocatalytic oxidation technology. The nano manganese dioxide has larger specific surface area, so that the efficiency is higher when the nano manganese dioxide is used for catalyzing and purifying formaldehyde.
The plant fiber is mainly generated through photosynthesis, approximately 2000 million tons of plant fiber are generated on the earth every year, the plant fiber is the most abundant renewable natural polymer resource in the nature, has the characteristics of wide raw material source, renewability, biodegradability, biocompatibility and the like, and is considered as an important resource of sustainable development materials. Different oxidation systems are selected to oxidize fibers, and primary hydroxyl at the C6 position of glucose is selectively oxidized into carboxyl, so that the polysaccharide polymer can be oxidized, and the yield can reach 95 percent at most.
Disclosure of Invention
The invention provides a formaldehyde-purifying fiber material and a preparation method thereof. The methodThe method adopts different oxidation systems to carry out oxidation modification on the fiber to obtain the fiber containing carboxyl, Mn2+The fiber of the in-situ growth nano manganese dioxide is obtained by loading the fiber through ion exchange and electrostatic adsorption, adding an oxidant and oxidizing.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a fiber/nano manganese dioxide composite material comprises the following steps:
(1) pretreating the fiber raw material
Carrying out selective oxidation treatment on the fiber raw material, and washing the fiber raw material to be neutral to obtain oxidized fiber;
(2) preparation of composite materials
Washing the oxidized fiber to neutrality after diluted acid treatment, and reacting with Mn2+And uniformly mixing and stirring the solution, adding an oxidant for reaction, washing and drying to finally obtain the in-situ grown nano manganese dioxide fiber.
In the step (1), the fibers are paper pulp fibers, bast fibers, seed fibers, tencel fibers, viscose fibers, modal fibers and the like.
In the step (1), the selective oxidation treatment adopts the following oxidation system: TEMPO/NaClO/NaBr, TEMPO/Ca (OCl)2KBr, TEMPO/NaOCl/ultrasound, HNO3/H3PO4-NaNO3Catalase/hydrogen peroxide/TEMPO, laccase/TEMPO/O2、NaIO4-NaClO2TCCA/NHPI/anthraquinone/NaBr, etc.
In the step (2), the Mn2+The solution is MnSO4、MnCl2Or (CH)3COO)2Mn solution, Mn2+The concentration is 0.005-0.5mol/L, and the stirring time is 0.1-12 h.
In the step (2), the oxidant is H2O2、KMnO4Or K2FeO4Oxidizing agent and Mn2+In a molar ratio of from 0.5:1 to 5: 1.
In the step (2), the concentration of the fiber is 0.1-5 wt%, and the stirring speed is 200-1500 rpm.
In the step (2), the reaction temperature is 10-90 ℃ and the reaction time is 0.05-12 h.
In the step (2), the dilute acid is HCl or H2SO4Or HNO3The concentration of dilute acid is 0.005-0.5mol/L, and the treatment time is 1-24 h; the washing is carried out until the washing liquid has no color change; the drying temperature is between room temperature and 100 ℃, and the drying time is 4-24 h.
The fiber/nano manganese dioxide composite material prepared by the method can be applied to purifying formaldehyde.
The invention selects the fiber which is selectively oxidized by different oxidation systems and is rich in carboxyl, and Mn2+After the solution is mixed and stirred uniformly, Mn is adsorbed on the surface of the fiber containing hydroxyl and carboxyl due to the electrostatic action2+While H in the carboxyl group+With Mn2+Ion exchange is carried out, and the fiber of the nano manganese dioxide growing in situ is obtained after the oxidant is added for reaction. The product has the advantages of the fiber and the nano manganese dioxide, and water enriched on the surface of the fiber is easy to dissociate into OH free radicals to participate in the reaction of oxidizing formaldehyde due to the easy moisture absorption of the fiber, so that the effect of catalytic purification of formaldehyde by the nano manganese dioxide is enhanced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts the fiber as the raw material, especially the plant fiber, has wide source, regeneration, biodegradability, green and environmental protection, can selectively oxidize the fiber by selecting various oxidation systems, and has wide range of reaction conditions and high reaction efficiency.
(2) Mn in the invention2+Performing ion exchange and electrostatic adsorption with the fiber, adding an oxidant for oxidation, and growing nano manganese dioxide on the fiber in situ; the nano manganese dioxide particles have narrow particle size distribution range, and are uniformly distributed on the surface of the fiber and are not easy to fall off.
(3) The fiber surface of the invention is rich in hydroxyl, and water generated by moisture absorption can be dissociated into OH free radicals by the nano manganese dioxide to participate in the reaction of oxidizing formaldehyde, thereby enhancing the effect of catalyzing and purifying formaldehyde by the nano manganese dioxide.
(4) The product obtained by the method has the excellent performances of both fiber and nano manganese dioxide, can be processed into a wood functional material with both decoration and functionality, is used for home decoration and air filtration purification, can particularly catalyze and purify formaldehyde in a dark room, and enriches the application field of nano manganese dioxide.
Drawings
Fig. 1 is an SEM image of the fiber/nano manganese dioxide composite obtained in example 1.
Fig. 2 is an SEM image of the fiber/nano manganese dioxide composite obtained in example 2.
Fig. 3 is an XRD pattern of the fiber/nano manganese dioxide composite obtained in example 1.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the specific embodiments and the accompanying drawings, but the scope of the present invention is not limited thereto.
Example 1
A preparation method of a formaldehyde-purifying fiber material specifically comprises the following steps:
(1) pre-treated fibers
Selectively oxidizing and bleaching the eucalyptus chemical pulp fiber by using a TEMPO/NaClO/NaBr system, and washing to be neutral to obtain an oxidized fiber;
(2) preparation of formaldehyde-purifying fiber material
Subjecting the oxidized fiber to 0.1mol/L of H2SO4Soaking for 1h, washing to neutrality, and adding MnCl at 0.05mol/L2Stirring the solution for 1h, and adding KMnO4Solution, KMnO4With MnCl2The molar ratio of the components is 1.5:1, the fiber concentration is 1 wt%, the stirring speed is 800rpm, the reaction temperature is 50 ℃, the reaction time is 20min, the fiber is washed after the reaction is finished until the washing liquid has no color change, and the fiber is dried at 40 ℃ for 12h to obtain the in-situ growth nano manganese dioxide fiber.
The scanning electron microscope image of the obtained fiber/nano manganese dioxide composite material is shown in fig. 1, and the nano manganese dioxide grown in situ on the fiber surface can be clearly seen through the fig. 1, wherein the nano manganese dioxide is spherical and is uniformly and densely distributed on the fiber surface.
The XRD pattern of the obtained fiber/nano manganese dioxide composite material is shown in fig. 3, and it can be clearly seen from fig. 3 that the characteristic diffraction peaks of cellulose and nano manganese dioxide are evident near 16.0 °, 22.0 °, 36.8 °, 43.0 °, 55.0 °, and 66.1 ° 2 θ.
The obtained fiber/nano manganese dioxide composite material is used for catalyzing and purifying formaldehyde, 0.6g/L formaldehyde solution is volatilized freely in a closed environment, the fiber/nano manganese dioxide composite material catalyzes and purifies the formaldehyde in the gas, and the formaldehyde removal amount is 60.06 mg/g.
Example 2
A preparation method of a formaldehyde-purifying fiber material specifically comprises the following steps:
(1) pre-treated fibers
Selecting laccase/TEMPO/O2Oxidizing and bleaching poplar chemical pulp fiber selectively by a system, and washing to be neutral to obtain oxidized fiber;
(2) preparation of formaldehyde-purifying fiber material
Soaking the oxidized fiber in 0.3mol/L HCl for 1h, washing to neutrality, and adding MnSO at 0.1mol/L4Stirring the solution for 3h, and adding K2FeO4，K2FeO4With MnSO4The molar ratio of the components is 1:1, the fiber concentration is 2 wt%, the stirring speed is 1000rpm, the reaction temperature is 30 ℃, the reaction time is 30min, the fiber is washed by deionized water after the reaction is finished until the washing liquid has no color change, and the fiber is dried for 8h at the temperature of 80 ℃ to obtain the fiber of the in-situ grown nano manganese dioxide.
The scanning electron microscope image of the obtained fiber/nano manganese dioxide composite material is shown in fig. 2, and the nano manganese dioxide grown in situ on the fiber surface can be clearly seen through the image 2, and due to the existence of iron element, the nano manganese dioxide is rod-shaped and is uniformly and densely distributed on the fiber surface. 0.6g/L formaldehyde solution is volatilized freely in a closed environment, the fiber/nano manganese dioxide composite material catalyzes and purifies the formaldehyde in the gas, and the formaldehyde removal amount is 55.46 mg/g.
Example 3
A formaldehyde-purifying fiber material and a preparation method thereof specifically comprise the following steps:
(1) pre-treated fibers
Selectively oxidizing tencel fiber by using a TCCA/NHPI/anthraquinone/NaBr system, and washing to be neutral to obtain oxidized fiber;
(2) preparation of formaldehyde-purifying fiber material
The oxidized fiber is treated by 0.05mol/L HNO3Soaking for 24 hr, washing to neutrality at 0.005mol/L (CH)3COO)2Stirring Mn solution for 5H, and adding H2O2，H2O2And (CH)3COO)2The molar ratio of Mn is 3:1, the fiber concentration is 5 wt%, the stirring speed is 200rpm, the reaction temperature is 10 ℃, the reaction time is 240min, the fiber is washed after the reaction is finished until the color of a washing solution is not changed, and the fiber is dried for 4h at 100 ℃ to obtain the in-situ growth nano manganese dioxide fiber.
And obtaining the fiber/nano manganese dioxide composite material after reaction, wherein nano manganese dioxide particles are spherical, are uniformly and densely distributed on the surface of the fiber, and have the effect of catalyzing and purifying formaldehyde.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (9)
1. The preparation method of the fiber/nano manganese dioxide composite material is characterized by comprising the following steps of:
(1) pretreating the fiber raw material
Carrying out selective oxidation treatment on the fiber raw material, and washing the fiber raw material to be neutral to obtain oxidized fiber;
the oxidation system adopted by the selective oxidation treatment is TEMPO/NaClO/NaBr, TEMPO/Ca (OCl)2KBr, TEMPO/NaOCl/ultrasound, HNO3/H3PO4-NaNO3Catalase/hydrogen peroxide/TEMPO,laccase/TEMPO/O2、NaIO4-NaClO2Or TCCA/NHPI/anthraquinone/NaBr;
(2) preparation of composite materials
Washing the oxidized fiber to neutrality after diluted acid treatment, and reacting with Mn2+And uniformly mixing and stirring the solution, adding an oxidant for reaction, washing and drying to finally obtain the in-situ grown nano manganese dioxide fiber.
2. The method according to claim 1, wherein in step (1), the fibers are pulp fibers, bast fibers, seed fibers, tencel fibers, viscose fibers or modal fibers.
3. The method according to claim 1, wherein in step (2), the Mn is2+The solution is MnSO4、MnCl2Or (CH)3COO)2Mn solution, Mn2+The concentration is 0.005-0.5 mol/L.
4. The method according to claim 1, 2 or 3, wherein in step (2), the oxidizing agent is H2O2、KMnO4Or K2FeO4Oxidizing agent and Mn2+In a molar ratio of from 0.5:1 to 5: 1.
5. The method as claimed in claim 4, wherein in the step (2), the concentration of the fiber is 0.1-5 wt%, and the stirring rate is 200-1500 rpm.
6. The method according to claim 5, wherein in the step (2), the reaction temperature is 10-90 ℃ and the reaction time is 0.05-12 h.
7. The method of claim 6, wherein in the step (2), the dilute acid is HCl or H2SO4Or HNO3The concentration of dilute acid is 0.005-0.5mol/L, and the treatment time is 1-24 h; the washing is carried out until the washing liquid has no color change;the drying temperature is between room temperature and 100 ℃, and the drying time is 4-24 h.
8. A fibre/nano manganese dioxide composite material prepared by the method of any one of claims 1 to 7.
9. Use of the fiber/nano-manganese dioxide composite material according to claim 8 for purifying formaldehyde.
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| CN108786925A (en) * | 2018-06-25 | 2018-11-13 | 福州大学 | A kind of preparation method of manganese and oxygen compound/composite material of plant fiber |
| CN109955336B (en) * | 2019-03-15 | 2021-02-12 | 华南理工大学 | Wood/nano LDHs flame-retardant material and preparation method thereof |
| CN111672478A (en) * | 2020-04-29 | 2020-09-18 | 南京尚易环保科技有限公司 | Formaldehyde-removing manganese oxide three-dimensional porous material and preparation method thereof |
| CN111921557B (en) * | 2020-06-19 | 2024-06-04 | 北京工业大学 | Device and method for removing formaldehyde by using nano friction charge reinforced manganese oxide/polymer composite material |
| CN112295602B (en) * | 2020-11-25 | 2022-09-27 | 嘉兴学院 | Preparation method and application of leather fiber-loaded active manganese dioxide catalytic material |
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