CN109944060A - A kind of nonwoven cloth material and preparation method thereof of supported porous manganese dioxide rod-like nano enzyme - Google Patents
A kind of nonwoven cloth material and preparation method thereof of supported porous manganese dioxide rod-like nano enzyme Download PDFInfo
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Abstract
The present invention provides a kind of nonwoven cloth material and preparation method thereof of supported porous manganese dioxide rod-like nano enzyme, it is uniformly mixed the following steps are included: Cetyltrimethylammonium bromide is added in ethanol water, constants temperature on one side enuatrol or sodium salicylate solution is added dropwise while and stirs to being uniformly mixed, constant temperature stands de-bubble, obtains rod-shaped micelle；Liquor potassic permanganate will be added in rod-shaped micelle, heated constant temperature oscillating reactions obtains the modified rod-shaped micelle of MnO4；The modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, high temperature sintering removes lameller micelles, obtains porous manganese dioxide rod-like nano enzyme；It disperses porous manganese dioxide rod-like nano enzyme in ionic liquid, chemical fibre is added, is dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme.Non-woven fabrics prepared by the present invention is easy to use to hydrogen peroxide catalyzed high-efficient.
Description
Technical field
The invention belongs to field of nonwoven fabric technology, and in particular to a kind of nonwoven of supported porous manganese dioxide rod-like nano enzyme
Cloth material and preparation method thereof.
Background technique
Nano enzyme refers on nanoscale, can show the inorganic material of enzymatic property, and nano enzyme can be in mild life
The substrate of efficient catalytic enzyme under the conditions of reason results from the identical reaction product of native enzyme, and the substitute that can be used as enzyme is adjusted carefully
Born of the same parents' metabolism, for the diagnosing and treating of disease, nano enzyme is compared with native enzyme, with cheap, preparation process is simple, stablizes
The advantages such as property is good, cyclic utilization rate is high, there is good development prospect in terms of biologic medical.
Nano enzyme has cerium oxide nano enzyme, the iron-based nano enzyme of oxidation, cobalt oxide/copper oxide/manganese dioxide/five oxidations at present
For two vanadium as magnesia analogies and metal-based nano enzyme etc., nano enzyme can be by changing the size, structure, group of its nano material
Divide and surface modification comes adjuster catalytic activity and catalyst mechanism.The wound of nano enzyme disclosed in Chinese patent CN108420803A can
Patch, preparation method and application method, by graphene quantum dot, ceria, nitrogen carbide or carbon with Mimetic Peroxidase
Change nitrogen and gold nano grain compound is attached on medical cotton, it is specific the preparation method comprises the following steps: fixed square on negative pressure leaching device
0.2-2mg/mL nanometers of enzyme aqueous solutions are added on the medical cotton of square by the medical cotton of shape, are passed it through by suction filtration medical
Cotton, the repetition process are fully absorbed by cotton fabric up to nano enzyme, then take out medical cotton, dry, by the nanometer after drying
Enzyme medical cotton is fixed on adhesive plaster, obtains nano enzyme adhesive bandage.Nanometer is prepared in situ disclosed in Chinese patent CN107723284A
The method of enzyme membrane, comprising the following steps: by polytetrafluoroethylene film, polyvinylidene fluoride film, PVDF membrane, PS membrane or gather
Ether sulfone original film carries out corona treatment under nitrogen atmosphere, is put into acrylic acid solution and impregnates, and then takes out and is placed in two panels glass
Among glass plate, heat polymerization is carried out in a vacuum drying oven, obtains the film of film surface grafting polyacrylic acid, it then will grafting
The film of polyacrylic acid impregnates in MOFs precursor solution, make metal ion in precursor solution by on polyacrylic acid
The coordination of carboxyl is assembled to film surface, and organic ligand solution and enzyme solution, co-precipitation one are then added into precursor solution
It takes the film out, rinses after the section time, freeze-drying or natural drying obtain the nanometer enzyme membrane of load nano enzyme.By above-mentioned existing it is found that
Nano enzyme can be attached to fiber film surface by way of by in-situ preparation and absorption, high performance nano enzyme base is prepared
Nonwoven cloth material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of non-woven fabrics materials of supported porous manganese dioxide rod-like nano enzyme
Material and preparation method thereof, porous porous manganese dioxide rod-like nano enzyme is prepared using rod-shaped micelle as mold in the present invention, more
Hole manganese dioxide rod-like nano enzyme has similar hydrogen peroxide enzyme viability, and stability is good, and being dispersed in non-woven fabrics can
The nonwoven cloth material haveing excellent performance is prepared.
In order to solve the above technical problems, the technical scheme is that
A kind of nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme, the supported porous manganese dioxide is rodlike to be received
The nonwoven cloth material of rice enzyme includes porous manganese dioxide rod-like nano enzyme, and the porous manganese dioxide rod-like nano enzyme uses micella
Template is prepared.
As a preferred embodiment of the above technical solution, the micella is self-assembly of rodlike for Cetyltrimethylammonium bromide
Micella.
The present invention also provides a kind of preparation methods of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme, including
Following steps:
(1) will Cetyltrimethylammonium bromide be added ethanol water in be uniformly mixed, on one side be added dropwise enuatrol or
Sodium salicylate solution one side constant temperature is stirred to being uniformly mixed, and constant temperature stands de-bubble, obtains rod-shaped micelle；
(2) liquor potassic permanganate will be added in the rod-shaped micelle of step (1) preparation, heated constant temperature oscillating reactions obtains height
The modified rod-shaped micelle of mangaic acid root；
(3) the modified rod-shaped micelle of the MnO4 of step (2) preparation is placed in high temperature sintering furnace, high temperature sintering removal
Lameller micelles obtains porous manganese dioxide rod-like nano enzyme；
(4) it disperses porous manganese dioxide rod-like nano enzyme prepared by step (3) in ionic liquid, it is fine that chemistry is added
Dimension, is dispersed with stirring to form stable fibrous suspension, removes ionic liquid, and pinprick reinforcement obtains supported porous manganese dioxide stick
The nonwoven cloth material of shape nano enzyme.
As a preferred embodiment of the above technical solution, in the step (1), Cetyltrimethylammonium bromide ethanol water
Volume ratio is 1:9-10, and the volume content that enuatrol or sodium salicylate alternative one account for total system is 10-12%.
As a preferred embodiment of the above technical solution, in the step (1), the temperature of constant temperature stirring is 35-40 DEG C, stirring rate
For 100-150r/min, the temperature that constant temperature is stood is 32-35 DEG C.
As a preferred embodiment of the above technical solution, in the step (2), cation exchange capacity of the rod-shaped micelle in system
For 2-3.
As a preferred embodiment of the above technical solution, in the step (2), the temperature of heated constant temperature oscillation is 80-90 DEG C, oscillation
Frequency is 200-250r/min, time 60-90min.
As a preferred embodiment of the above technical solution, in the step (3), the technique of high temperature sintering are as follows: with 5-10 DEG C/min's
Rate is warming up to 450-500 DEG C, is then warming up to 530-550 DEG C, heat preservation sintering 2-4h with the rate of 1-3 DEG C/min, then with 10-
The rate of 20 DEG C/min is warming up to 200-250 DEG C, is down to room temperature naturally.
As a preferred embodiment of the above technical solution, in the step (4), ionic liquid is ionic liquid (bmim) PF6.
As a preferred embodiment of the above technical solution, in the step (4), the nonwoven of supported porous manganese dioxide rod-like nano enzyme
The content of porous manganese dioxide rod-like nano enzyme is 1.5-6wt% in cloth material.
Compared with prior art, the invention has the following advantages:
(1) functional material in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme prepared by the present invention is more
Hole manganese dioxide rod-like nano enzyme, porous manganese dioxide rod-like nano enzyme contain porous meso-hole structure, large specific surface area, adsorption energy
Power is strong, and surface can be high, high to the catalytic activity of hydrogen peroxide, and conversion efficiently, can reach good using seldom amount
Bactericidal effect.
(2) the porous dioxy contained in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme prepared by the present invention
Changing manganese rod-like nano enzyme is prepared based on template, select Cetyltrimethylammonium bromide surfactant and enuatrol or
Sodium salicylate is prepared, and the rod-shaped micelle of preparation has natural affine performance to MnO4, and MnO4 is allow to exist
The surface of micella forms more close film, then goes also to form manganese dioxide particle while removing template through high temperature sintering,
Then it is prepared with porous mesoporous porous manganese dioxide nano enzyme.
(3) nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme prepared by the present invention is by porous manganese dioxide stick
Shape nano enzyme and fiber make to be uniformly distributed porous manganese dioxide rod-like nano enzyme in non-woven fabrics after mixing in pinprick reinforcement,
It is that good bactericidal property is all had inside and outside non-woven fabrics, functional stabilization is good.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) Cetyltrimethylammonium bromide that volume ratio is 1:9 is added in the ethanol water that volume ratio is 3:1 and is mixed
It closes uniformly, the sodium oleate solution for accounting for that the volume content of total system is 10% is added dropwise on one side, on one side at 35 DEG C, with 100r/min's
Revolving speed constant temperature is stirred to being uniformly mixed, and constant temperature stands de-bubble at 32 DEG C, obtains rod-shaped micelle.
(2) cation exchange capacity according to rod-shaped micelle in system is 2, molten by potassium permanganate is added in rod-shaped micelle
Liquid, with the rate heated constant temperature oscillating reactions 60min of 200r/min, obtains the modified rod-shaped micelle of MnO4 at 80 DEG C.
(3) the modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, is warming up to 450 with the rate of 5 DEG C/min
DEG C, 530 DEG C, heat preservation sintering 2h then are warming up to the rate of 1 DEG C/min, then be warming up to 200 DEG C with the rate of 10 DEG C/min, from
It is so down to room temperature, lameller micelles is removed, obtains porous manganese dioxide rod-like nano enzyme.
(4) it disperses porous manganese dioxide rod-like nano enzyme in ionic liquid (bmim) PF6, addition length is 3-10cm
Chemical fibre, be dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous two
The nonwoven cloth material of manganese oxide rod-like nano enzyme, wherein more in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content of hole manganese dioxide rod-like nano enzyme is 1.5wt%.
Embodiment 2:
(1) volume ratio is added in the Cetyltrimethylammonium bromide that volume ratio is 1:10 is in the ethanol water of 4:1
It is uniformly mixed, the sodium salicylate solution for accounting for that the volume content of total system is 12% is added dropwise on one side, on one side at 40 DEG C, with 150r/
The revolving speed constant temperature of min is stirred to being uniformly mixed, and constant temperature stands de-bubble at 35 DEG C, obtains rod-shaped micelle.
(2) cation exchange capacity according to rod-shaped micelle in system is 3, molten by potassium permanganate is added in rod-shaped micelle
Liquid, with the rate heated constant temperature oscillating reactions 90min of 250r/min, obtains the modified rod-shaped micelle of MnO4 at 90 DEG C.
(3) the modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, is warming up to 500 with the rate of 10 DEG C/min
DEG C, 550 DEG C, heat preservation sintering 4h then are warming up to the rate of 3 DEG C/min, then be warming up to 250 DEG C with the rate of 20 DEG C/min, from
It is so down to room temperature, lameller micelles is removed, obtains porous manganese dioxide rod-like nano enzyme.
(4) it disperses porous manganese dioxide rod-like nano enzyme in ionic liquid (bmim) PF6, addition length is 3-10cm
Chemical fibre, be dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous two
The nonwoven cloth material of manganese oxide rod-like nano enzyme, wherein more in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content of hole manganese dioxide rod-like nano enzyme is 6wt%.
Embodiment 3:
(1) ethanol water that volume ratio is 3.2:1 is added in the Cetyltrimethylammonium bromide that volume ratio is 1:9.5
In be uniformly mixed, on one side be added dropwise account for total system volume content be 11% sodium oleate solution, on one side at 38 DEG C, with 140r/
The revolving speed constant temperature of min is stirred to being uniformly mixed, and constant temperature stands de-bubble at 33 DEG C, obtains rod-shaped micelle.
(2) cation exchange capacity according to rod-shaped micelle in system is 2.5, and potassium permanganate will be added in rod-shaped micelle
Solution, with the rate heated constant temperature oscillating reactions 75min of 230r/min, obtains the modified rodlike glue of MnO4 at 85 DEG C
Beam.
(3) the modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, is warming up to 480 with the rate of 8 DEG C/min
DEG C, 535 DEG C, heat preservation sintering 3.5h then are warming up to the rate of 2.5 DEG C/min, then be warming up to 240 with the rate of 15 DEG C/min
DEG C, it is down to room temperature naturally, removes lameller micelles, obtains porous manganese dioxide rod-like nano enzyme.
(4) it disperses porous manganese dioxide rod-like nano enzyme in ionic liquid (bmim) PF6, addition length is 3-10cm
Chemical fibre, be dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous two
The nonwoven cloth material of manganese oxide rod-like nano enzyme, wherein more in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content of hole manganese dioxide rod-like nano enzyme is 4.5wt%.
Embodiment 4:
(1) ethanol water that volume ratio is 3.6:1 is added in the Cetyltrimethylammonium bromide that volume ratio is 1:9.2
In be uniformly mixed, on one side be added dropwise account for total system volume content be 10-12% enuatrol or sodium salicylate solution, exist on one side
It at 39 DEG C, is stirred with the revolving speed constant temperature of 130r/min to being uniformly mixed, constant temperature stands de-bubble at 34 DEG C, obtains rod-shaped micelle.
(2) cation exchange capacity according to rod-shaped micelle in system is 2.6, and potassium permanganate will be added in rod-shaped micelle
Solution, with the rate heated constant temperature oscillating reactions 75min of 210r/min, obtains the modified rodlike glue of MnO4 at 88 DEG C
Beam.
(3) the modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, is warming up to 480 with the rate of 9 DEG C/min
DEG C, 545 DEG C, heat preservation sintering 3.5h then are warming up to the rate of 2.5 DEG C/min, then be warming up to 225 with the rate of 17 DEG C/min
DEG C, it is down to room temperature naturally, removes lameller micelles, obtains porous manganese dioxide rod-like nano enzyme.
(4) it disperses porous manganese dioxide rod-like nano enzyme in ionic liquid (bmim) PF6, addition length is 3-10cm
Chemical fibre, be dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous two
The nonwoven cloth material of manganese oxide rod-like nano enzyme, wherein more in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content of hole manganese dioxide rod-like nano enzyme is 3.5wt%.
Embodiment 5:
(1) Cetyltrimethylammonium bromide that volume ratio is 1:9 is added in the ethanol water that volume ratio is 4:1 and is mixed
It closes uniformly, the sodium salicylate solution for accounting for that the volume content of total system is 10% is added dropwise on one side, on one side at 35 DEG C, with 150r/min
Revolving speed constant temperature stir to be uniformly mixed, at 32 DEG C constant temperature stand de-bubble, obtain rod-shaped micelle.
(2) cation exchange capacity according to rod-shaped micelle in system is 3, molten by potassium permanganate is added in rod-shaped micelle
Liquid, with the rate heated constant temperature oscillating reactions 60min of 250r/min, obtains the modified rod-shaped micelle of MnO4 at 80 DEG C.
(3) the modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, is warming up to 450 with the rate of 10 DEG C/min
DEG C, 530 DEG C, heat preservation sintering 4h then are warming up to the rate of 3 DEG C/min, then be warming up to 250 DEG C with the rate of 10 DEG C/min, from
It is so down to room temperature, lameller micelles is removed, obtains porous manganese dioxide rod-like nano enzyme.
(4) it disperses porous manganese dioxide rod-like nano enzyme in ionic liquid (bmim) PF6, addition length is 3-10cm
Chemical fibre, be dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous two
The nonwoven cloth material of manganese oxide rod-like nano enzyme, wherein more in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content of hole manganese dioxide rod-like nano enzyme is 1.5wt%.
Embodiment 6:
(1) volume ratio is added in the Cetyltrimethylammonium bromide that volume ratio is 1:10 is in the ethanol water of 3:1
It is uniformly mixed, the sodium oleate solution for accounting for that the volume content of total system is 12% is added dropwise on one side, on one side at 35 DEG C, with 150r/min
Revolving speed constant temperature stir to be uniformly mixed, at 32 DEG C constant temperature stand de-bubble, obtain rod-shaped micelle.
(2) cation exchange capacity according to rod-shaped micelle in system is 3, molten by potassium permanganate is added in rod-shaped micelle
Liquid, with the rate heated constant temperature oscillating reactions 60min of 250r/min, obtains the modified rod-shaped micelle of MnO4 at 80 DEG C.
(3) the modified rod-shaped micelle of MnO4 is placed in high temperature sintering furnace, is warming up to 450 with the rate of 10 DEG C/min
DEG C, 530 DEG C, heat preservation sintering 4h then are warming up to the rate of 3 DEG C/min, then be warming up to 250 DEG C with the rate of 10 DEG C/min, from
It is so down to room temperature, lameller micelles is removed, obtains porous manganese dioxide rod-like nano enzyme.
(4) it disperses porous manganese dioxide rod-like nano enzyme in ionic liquid (bmim) PF6, addition length is 3-10cm
Chemical fibre, be dispersed with stirring to form stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous two
The nonwoven cloth material of manganese oxide rod-like nano enzyme, wherein more in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content of hole manganese dioxide rod-like nano enzyme is 5.5wt%.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme, it is characterised in that: the supported porous dioxy
The nonwoven cloth material for changing manganese rod-like nano enzyme includes porous manganese dioxide rod-like nano enzyme, the porous manganese dioxide rod-like nano
Enzyme is prepared using Micellar Gel method.
2. a kind of nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 1, feature exist
In: the micella is the rod-shaped micelle that Cetyltrimethylammonium bromide is self-assembly of.
3. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme described in claims 1 or 2
Method, which comprises the following steps:
(1) Cetyltrimethylammonium bromide is added in ethanol water and is uniformly mixed, enuatrol or bigcatkin willow are added dropwise on one side
Acid sodium solution one side constant temperature is stirred to being uniformly mixed, and constant temperature stands de-bubble, obtains rod-shaped micelle；
(2) liquor potassic permanganate will be added in the rod-shaped micelle of step (1) preparation, heated constant temperature oscillating reactions obtains permanganic acid
The modified rod-shaped micelle of root；
(3) the modified rod-shaped micelle of the MnO4 of step (2) preparation is placed in high temperature sintering furnace, high temperature sintering removes stratiform
Micella obtains porous manganese dioxide rod-like nano enzyme；
(4) it disperses porous manganese dioxide rod-like nano enzyme prepared by step (3) in ionic liquid, chemical fibre is added, stirs
It mixes dispersion and forms stable fibrous suspension, remove ionic liquid, pinprick reinforcement obtains supported porous manganese dioxide rod-like nano
The nonwoven cloth material of enzyme.
4. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (1), the volume ratio of Cetyltrimethylammonium bromide ethanol water is 1:9-10, oil
The volume content that sour sodium or sodium salicylate alternative one account for total system is 10-12%.
5. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (1), the temperature of constant temperature stirring is 35-40 DEG C, stirring rate 100-150r/min, permanent
The temperature that temperature is stood is 32-35 DEG C.
6. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (2), cation exchange capacity of the rod-shaped micelle in system is 2-3.
7. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (2), the temperature of heated constant temperature oscillation is 80-90 DEG C, frequency of oscillation 200-250r/
Min, time 60-90min.
8. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (3), the technique of high temperature sintering are as follows: 450-500 is warming up to the rate of 5-10 DEG C/min
DEG C, it then is warming up to 530-550 DEG C, heat preservation sintering 2-4h with the rate of 1-3 DEG C/min, then with the rate liter of 10-20 DEG C/min
Temperature is down to room temperature to 200-250 DEG C naturally.
9. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (4), ionic liquid is ionic liquid (bmim) PF6.
10. a kind of preparation side of the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme according to claim 3
Method, it is characterised in that: in the step (4), porous dioxy in the nonwoven cloth material of supported porous manganese dioxide rod-like nano enzyme
The content for changing manganese rod-like nano enzyme is 1.5-6wt%.
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Application publication date: 20190628 |