CN110433804B - Method for preparing silver oxide-doped manganese oxide nanowire network based on electrostatic spinning and application of silver oxide-doped manganese oxide nanowire network in catalytic decomposition of formaldehyde - Google Patents
Method for preparing silver oxide-doped manganese oxide nanowire network based on electrostatic spinning and application of silver oxide-doped manganese oxide nanowire network in catalytic decomposition of formaldehyde Download PDFInfo
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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 112
- 239000002070 nanowire Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 12
- 239000004332 silver Substances 0.000 title claims abstract description 12
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 90
- 239000000243 solution Substances 0.000 claims abstract description 73
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011572 manganese Substances 0.000 claims abstract description 24
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 19
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
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- 238000002347 injection Methods 0.000 claims abstract description 4
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- 239000012286 potassium permanganate Substances 0.000 claims description 18
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- 239000007788 liquid Substances 0.000 claims description 8
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- 238000002360 preparation method Methods 0.000 abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 8
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- KIIUTKAWYISOAM-UHFFFAOYSA-N silver sodium Chemical compound [Na].[Ag] KIIUTKAWYISOAM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B01J35/61—
Abstract
The invention discloses a method for preparing a silver oxide-doped manganese oxide nanowire network based on electrostatic spinning and application of the silver oxide-doped manganese oxide nanowire network in catalytic decomposition of formaldehyde, wherein the method comprises the following steps: the method comprises the following steps: mixing Mn (CH)3COO)2Adding the solution into a PVA solution in a room temperature state, and magnetically stirring at room temperature to obtain an electrostatic spinning precursor solution; step two: pushing the injector piston by using the electrostatic spinning precursor solution through an injection pump to carry out electrostatic spinning; step three: the spun sample is firstly put into high-temperature air for high-temperature calcination, and then KMnO is adopted4Soaking the obtained nanowire network by a solution soaking method; step four: and (3) dropping the silver nanowire dispersion on a nanowire network, drying, and treating a sample in which the silver nanowire is dropped by using oxygen plasma, thereby doping the silver oxide nanowire. The method has the advantages of simple required equipment, safe and convenient connection process and short preparation period, realizes the doping of the silver oxide and improves the catalytic effect.
Description
Technical Field
The invention belongs to the field of nano material manufacturing, and relates to a method for preparing a silver oxide-doped manganese oxide nanowire network based on electrostatic spinning and application of the silver oxide-doped manganese oxide nanowire network in catalytic decomposition of formaldehyde.
Background
The problem of indoor air pollution caused by formaldehyde is becoming more serious, and how to remove formaldehyde efficiently has become a great research hotspot. Nowadays, a series of researches on catalytic degradation of formaldehyde are internationally carried out, and mainly comprise a recovery method and a decomposition and purification method. The recovery method separates formaldehyde from gas to obtain formaldehyde with higher concentration, and the formaldehyde is applied to industrial production, but the recovery method has higher cost and is easy to cause secondary pollution in the treatment process. The decomposition and purification method completely decomposes formaldehyde into non-toxic and harmless carbon dioxide and water by using chemical reaction through methods such as ultraviolet light oxidation, biodegradation, catalyst-assisted decomposition and the like. The decomposition and purification method can remove formaldehyde efficiently without generating secondary pollution, and is the focus of the current research. Manganese oxide, as a transition metal oxide, has excellent catalytic performance, high activity, low cost, no toxicity and other advantages, and has been favored and valued by more and more researchers. In order to achieve good catalytic performance, the catalyst generally requires a characteristic of large specific surface area, so people usually use manganese oxide nano materials to realize catalytic degradation of formaldehyde.
Among the preparation processes of various nano materials, the electrostatic spinning method is the simplest method for preparing the nanowire structure, and the prepared manganese oxide nanowire network has a large specific surface area and a high length-diameter ratio and has a wide application prospect in the field of catalysis. The manganese oxide nanowire network obtained by simply adopting the electrostatic spinning method is usually not obvious in catalytic effect on formaldehyde due to low long diameter, and how to improve the catalytic effect of the manganese oxide on the formaldehyde becomes the focus of research of researchers in the field.
Disclosure of Invention
Aiming at the problems of the method for preparing the manganese oxide nanowire catalytic formaldehyde by the electrostatic spinning method, the invention provides a method for preparing a silver oxide-doped manganese oxide nanowire network based on electrostatic spinning and application of the method in catalytic decomposition of formaldehyde.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a silver oxide doped manganese oxide nanowire network based on electrostatic spinning comprises the following steps:
the method comprises the following steps: mixing Mn (CH)3COO)2Adding the solution into PVA solution at room temperature, and magnetically stirring at room temperature to obtain uniform, transparent and viscous electrostatic spinning precursorA solution, wherein: the Mn (CH)3COO)2The concentration of the solution is 0.25-0.3 g/mL, the concentration of the PVA solution is 0.1-0.15 g/mL, Mn (CH)3COO)2The volume ratio of the solution to the PVA solution is 9: 5; stirring for 1-2 h;
step two: and (2) adopting an electrostatic spinning device, pushing an injector piston by using the electrostatic spinning precursor solution prepared in the step one through an injection pump, and carrying out electrostatic spinning, wherein: in the electrostatic spinning process, a 1 ml injector is selected as a spinning solution container, the flow rate of the spinning solution is 0.25-0.30 ml/h, the spinning voltage is 18-20 kV, and the distance between a spinning head and a collecting plate is 15-20 cm;
step three: putting the spun sample obtained in the step two into high-temperature air for high-temperature calcination to ensure that PVA and Mn (CH) in the nanowire network3COO)2Decomposing to obtain manganese oxide, and using KMnO4Soaking the obtained nanowire network by a solution soaking method, wherein: in the high-temperature calcination process, the sample is heated to 800 ℃ from room temperature (20 ℃) at the heating rate of 2 ℃/min, then the sample is kept at the high temperature for 3-3.5 hours, and finally the sample is naturally cooled; the KMnO4The solution soaking method adopts KMnO with volume of 14 ml and 2 g/L4Putting the solution and the high-temperature calcined nanowire network into a hydrothermal reaction kettle, heating the system from room temperature to 150-200 ℃ at a heating rate of 2 ℃/min, then preserving heat at the high temperature for 5-5.5 hours to enable the solution to react fully, and finally naturally cooling;
step four: and C, dropping the silver nanowire dispersion liquid on the nanowire network obtained in the step three, drying, and treating a sample in which the silver nanowire is dropped by using oxygen plasma to further realize doping of the silver oxide nanowire, wherein: the concentration of the silver nanowire dispersion liquid is 2 mg/mL, and the using amount is 15 mu L; the drying temperature is 60 ℃; the oxygen plasma treatment time was 90 s.
The PVA/Mn (CH) is used in the invention3COO)2The mixed solution is used as spinning solution, and PVA and Mn (CH) are subjected to subsequent high-temperature calcination3COO)2Decomposing to form high-valence manganese oxide, and using KMnO4Method for increasing high-valence manganese (Mn) by solution soaking method4+) Proportion of (2), higher oxidationManganese has better catalytic performance, and finally, the obtained manganese oxide nanowires are doped by using the silver nanowire dispersion liquid, so that the specific surface area and the length-diameter ratio are improved, and the catalytic performance of the nanowire network structure on formaldehyde is further improved.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the electrostatic spinning method to obtain the manganese oxide nano-wire with extremely large specific surface area and extremely high length-diameter ratio, and can realize the catalytic decomposition of formaldehyde.
2. The invention utilizes a high-temperature calcination method and KMnO4The solution soaking method is used for two-step treatment to obtain high-valence manganese oxide, and the catalytic performance of the manganese oxide on formaldehyde is further improved.
3. The invention realizes the doping of the silver oxide, obtains the silver oxide/manganese oxide nanowire network structure by using the silver nanowire dispersion liquid, does not change the crystal structure of the manganese oxide by doping, realizes the oxidation of the silver nanowire by using the oxygen plasma, efficiently decomposes the formaldehyde, improves the catalytic effect, and has great advantages in a plurality of manganese oxide nanostructures and methods for catalytically decomposing the formaldehyde.
4. The invention has the advantages of simple required equipment, safe and convenient connection process and short preparation period.
Drawings
Fig. 1 is a schematic structural diagram of an electrostatic spinning device, wherein: 1-high voltage direct current power supply, 2-receiving plate, 3-injector, 4-injector metal needle, 5-spinning solution and 6-injector piston rod.
FIG. 2 shows KMnO without high temperature calcination4Solution soaked manganese oxide nanowire image, in the figure: a is the overall picture of the nanowire network, and b is a partial enlarged view of the nanowire connection part.
Fig. 3 is an image of a manganese oxide nanowire after high-temperature calcination, in which: a is the overall picture of the nanowire network, and b is a partial enlarged view of the nanowire connection part.
FIG. 4 shows the sample after passing through KMnO4The manganese oxide nanowire image after the solution soaking is as follows: a is the overall picture of the nanowire network, and b is a partial enlarged view of the nanowire connection part.
Fig. 5 is an image of a manganese oxide nanowire doped with silver oxide, in which: 1-manganese oxide nanowire network and 2-silver oxide nanowire network, wherein a is a whole graph of the nanowire network, and b is a local enlarged view of a nanowire connection part.
FIG. 6 is a diagram of a formaldehyde catalytic decomposition apparatus, in which: 1-formaldehyde solution, 2-nitrogen, 3-manganese oxide nanowire, 4-water stop clip and 5-absorption liquid.
FIG. 7 shows the high temperature calcination + KMnO4Mn of XRD test of manganese oxide nanowire soaked in solution4+Scale results, in the figure: a is the XRD test result after high-temperature calcination, and b is KMnO4And (4) XRD testing results after the solution is soaked.
FIG. 8 shows the catalytic effect of a manganese oxide nanowire network doped with silver oxide on formaldehyde, where a is the result of the present invention and b is the comparison of the catalytic effect of the present invention on formaldehyde with other methods in the field.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The invention provides a method for preparing a silver oxide-doped manganese oxide nanowire network based on electrostatic spinning, which uses Polyvinyl Alcohol (PVA) solution and Mn (CH)3COO)2Preparing electrostatic spinning precursor solution from the solution, and then calcining at high temperature and KMnO4Soaking in the solution, finally dispersing the silver nanowires in the manganese oxide nanowires, and carrying out oxygen plasma treatment to realize doping. The specific implementation steps are as follows:
(1) preparing a spinning solution: firstly, preparing an electrostatic spinning precursor solution. First, 3 g of Polyvinyl Alcohol (PVA) was weighed out and dissolved in 22.5 ml of deionized water, and the solution was magnetically stirred at 70 ℃ for 2.5 hours to obtain a uniform, transparent and viscous solution. Then, the heating is stopped, the PVA solution is naturally cooled, and the stirring is continued during the cooling process to ensure that the solution is still uniform. Then preparing Mn (CH)3COO)2Solution, weighing3 g Mn(CH3COO)2·4H2Solid O, dissolved in 10.5 ml deionized water. To Mn (CH)3COO)2·4H2After O is completely dissolved, Mn (CH)3COO)2The solution was added to the room temperature PVA solution and stirred magnetically at room temperature for 1.5 h. The above solutions are sealed by plastic films in the preparation process to prevent water loss. Finally, uniform, transparent and viscous electrostatic spinning precursor solution is obtained.
(2) Preparing nanowires through electrostatic spinning: sucking the spinning solution into an injector, and applying high voltage between a needle head of the injector and a receiving surface to carry out electrostatic spinning, wherein: the electrostatic spinning voltage is 18 kV, and the distance between the spinning head and the collecting plate is 15 cm. In the experiment, a 1 ml syringe is selected as a spinning solution container, a syringe piston is pushed by an injection pump to carry out spinning, and the flow rate of the spinning solution is 0.25 ml/h.
(3) High-temperature calcination of the nanowires: calcining the nanowire obtained by electrostatic spinning in high-temperature air to ensure that PVA and Mn (CH) in the nanowire network3COO)2Decomposing the manganese oxide into manganese oxide, and oxidizing the manganese oxide by oxygen in the air at high temperature to obtain high-valence manganese oxide. Wherein, the calcining conditions are as follows: heating from room temperature (20 ℃) to 800 ℃ at a heating rate of 2 ℃/min, then preserving the heat at the high temperature for 3 h, and finally naturally cooling.
（4）KMnO4Soaking in a solution: by adopting KMnO4The solution is soaked in the nanowire network after high-temperature calcination, and high-valence manganese oxide is obtained by utilizing the centering reaction between 7-valence Mn and 2-valence Mn. Wherein KMnO4The solution soaking method comprises the following specific steps: using KMnO of 14 ml and 2 g/L4Putting the solution and the sample into a hydrothermal reaction kettle, heating the system from room temperature to 150 ℃ at the heating rate of 2 ℃/min, then preserving heat for 5 hours at the high temperature to ensure that the solution is fully reacted, and finally naturally cooling.
(5) Doping: 0.1 mL of silver nanowire dispersion liquid is taken and added with 0.9 mL of absolute ethyl alcohol to be diluted into 2 mg/mL of silver nanowire dispersion liquid. Then the mixture is calcined at high temperature and KMnO4Soaking the manganese oxide nanowire samples in the solution, and dropwise adding 15 mu L of prepared silver sodium to each sampleDispersing rice noodles, and drying at 60 deg.C.
(6) And oxidizing the silver nanowires by using an oxygen plasma cleaning machine, treating for 90 s by using oxygen plasma, wherein the plasma generation power is 258 mA multiplied by 852V, and the air pressure in the cavity is 6.0 multiplied by 101 Pa, so that the doping of the silver oxide nanowires is realized.
The silver oxide doped manganese oxide nanowire network prepared by the method is shown in figure 5, and untreated, high-temperature calcined and KMnO are adopted in the same way as in figures 2, 3 and 4 respectively4Compared with a sample treated by solution soaking, the doped manganese oxide nanowire network has larger comparative area and length-diameter ratio, so that the catalytic decomposition effect on formaldehyde is better.
FIG. 7b shows the high temperature calcination + KMnO4Mn in manganese oxide nanowire network after solution soaking treatment4+The ratio of the manganese oxide nanowires was 26%, compared to the manganese oxide nanowire network of FIG. 7a, which only uses high-temperature calcination treatment (Mn)4+19 percent of the total weight of the powder), high-temperature calcination and KMnO are adopted4Sample Mn treated by solution immersion4+The proportion is higher, and the catalytic effect on formaldehyde is better.
FIG. 8a shows the result of catalytic decomposition of formaldehyde by a silver oxide-doped manganese oxide nanowire network, which is subjected to high-temperature calcination and KMnO4The decomposition rate of the silver oxide/manganese oxide nanowire network obtained by solution soaking treatment on formaldehyde is 93.7%, and the decomposition rate is not subjected to high-temperature calcination and KMnO4Compared with the undoped sample, the solution soaking treatment has more obvious decomposition effect on formaldehyde.
Fig. 8b shows the formaldehyde decomposition rate of the silver oxide/manganese oxide nanowire network of the present invention compared to manganese oxide nanostructures prepared by other methods in the art. As can be seen from the figure, compared with other preparation methods, the invention has more advantages on the catalytic decomposition effect of formaldehyde.
Claims (8)
1. A method for preparing a silver oxide-doped manganese oxide nanowire network based on electrostatic spinning is characterized by comprising the following steps:
the method comprises the following steps: mixing Mn (CH)3COO)2Adding the solution into a PVA solution in a room temperature state, and magnetically stirring at room temperature to obtain a uniform, transparent and viscous electrostatic spinning precursor solution;
step two: an electrostatic spinning device is adopted, the electrostatic spinning precursor solution prepared in the step one is utilized to push an injector piston through an injection pump, and electrostatic spinning is carried out;
step three: putting the spun sample obtained in the step two into high-temperature air for high-temperature calcination, and adopting KMnO4Soaking the obtained nanowire network by a solution soaking method, wherein in the high-temperature calcination process, the temperature of a sample is increased from room temperature to 800 ℃ at the heating rate of 2 ℃/min, then, the sample is kept at the high temperature for 3-3.5 h, and finally, the sample is naturally cooled; the KMnO4The solution soaking method comprises the following specific steps: mixing KMnO4Putting the solution and the high-temperature calcined nanowire network into a hydrothermal reaction kettle, heating the system from room temperature to 150-200 ℃ at a heating rate of 2 ℃/min, then preserving heat at the high temperature for 5-5.5 hours to enable the solution to react fully, and finally naturally cooling;
step four: and D, dropping the silver nanowire dispersion liquid on the nanowire network obtained in the step three, drying, and treating a sample to which the silver nanowire is dropped by using oxygen plasma, so as to realize doping of the silver oxide nanowire.
2. The method for preparing a network of silver oxide doped manganese oxide nanowires based on electrospinning according to claim 1, characterized in that the Mn (CH) is3COO)2The concentration of the solution is 0.25-0.3 g/mL, the concentration of the PVA solution is 0.1-0.15 g/mL, Mn (CH)3COO)2The volume ratio of the solution to the PVA solution was 9: 5.
3. The method for preparing the silver oxide doped manganese oxide nanowire network based on electrostatic spinning according to claim 1, characterized in that the stirring time is 1-2 h.
4. The method for preparing the silver oxide doped manganese oxide nanowire network based on electrostatic spinning according to claim 1, characterized in that in the electrostatic spinning process, a 1 mL injector is selected as a spinning solution container, the flow rate of the spinning solution is 0.25-0.30 mL/h, the spinning voltage is 18-20 kV, and the distance between a spinning head and a collecting plate is 15-20 cm.
5. The method for preparing the silver oxide doped manganese oxide nanowire network based on electrostatic spinning according to claim 1, characterized in that the concentration of the silver nanowire dispersion is 2 mg/mL and the amount is 15 μ L.
6. The method for preparing a silver oxide doped manganese oxide nanowire network based on electrospinning according to claim 1, characterized in that the drying temperature is 60 ℃.
7. The method for preparing a network of doped silver oxide nanowires based on electrospinning according to claim 1, characterized in that the oxygen plasma treatment time is 90 s.
8. Use of a network of silver oxide doped manganese oxide nanowires prepared by a process according to any one of claims 1 to 7 for the catalytic decomposition of formaldehyde.
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