CN105692701A - Zn<2+> doped MnO2-based catalyst nanorod and synthesizing method thereof - Google Patents
Zn<2+> doped MnO2-based catalyst nanorod and synthesizing method thereof Download PDFInfo
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- permanganate
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000002073 nanorod Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 229910003144 α-MnO2 Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 2
- ZZCNKSMCIZCVDR-UHFFFAOYSA-N barium(2+);dioxido(dioxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])(=O)=O ZZCNKSMCIZCVDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000004887 air purification Methods 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910006364 δ-MnO2 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Zn<2+> doped MnO2-based catalyst nanorod and a synthesizing method thereof.The diameter of the nanorod is 1-10 nanometers, the length of the nanorod is 10-200 nanometers, and the crystal form of the nanorod is alpha-MnO2.According to the Zn<2+> doped MnO2 catalyst nanorod and the synthesizing method thereof, the preparation technology is simple, the cost is low, the repeatability is good, and industrial production is easy; by means of the electrical property and nanostructure of the nanorod and the catalytic capacity to volatile organic compounds (VOCs), application in the fields of electronic appliances such as transparent conductive films, flexible display devices, thin film transistors, sensors and super-capacitors and nano material air purification is hopefully achieved.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to a kind of Zn2+Doping MnO2Catalyst based nanometer rods and synthetic method thereof。
Background technology
Atmospheric environment, as the key factor of human survival and development, is subject to people and payes attention to widely。Air quality is not only related to life and the safety of people, and has become and evaluated the important indicator developed in a healthy way in a city。Along with developing rapidly of National Industrial, the transition of natural resources is develop and useedd, atmospheric environment has been caused immeasurable pollution and destruction by the activity of the mankind, has severely impacted the health of people and the development of regional economy, therefore that the control of atmospheric pollution is very urgent。Volatile organic matter (VOCs) is as the by-product of China's industry high speed development, not only ecological environment is polluted (as being generated as photochemical fog, broken ring ozone layer and secondary organic aerosol (SOA)), and serious threat human health (such as respiratory disorder etc.)。Country is middle carrying out the pith that VOC (VOCs) preventing and controlling work as atmospheric pollution groupcontrol in " 12 planning "。Therefore, we need badly and to develop effective technology to process volatile organic contaminant。In the past few decades, obtain significant progress with the VOCs Treatment process that absorption method, photocatalytic method and heat catalytic oxidation method are representative, achieve certain effect, there is also some problems simultaneously。Such as the adsorption technology being representative with activated carbon, although its energy consumption is low, removal efficiency is high, but its adsorptive selectivity is poor, adsorbs easily saturated and not easily desorption, it is easy to cause secondary pollution, greatly limit it and apply further。With TiO2Quasiconductor is the photocatalysis technology of representative, although have Many researchers that its response range is widened visual field, but traditional photocatalytic mechanism research shows, very difficult its quantum efficiency that improves further, and TiO2In use, the easy carbon deposit in its surface, inactivation, therefore the application of photochemical catalytic oxidation VOCs technology remains a very long process。Heat catalytic oxidation technology, owing to having process waste gas efficiency height, do not have secondary pollution and be absent from adsorbing the advantages such as saturated, is subject to people and payes attention to widely。But, currently used wide High Efficiency Thermal catalyst is mainly carried noble metal, in short supply due to Precious Metals Resources, and Financial cost is high, and therefore we are necessary the catalyst studying cheap and easy to get, high activity and noble metal can be replaced to use。Manganese dioxide (MnO2) catalyst is widely present in nature, it is easy to get owing to it is cheap, environmental friendliness, it is subject to people's extensive concern。In a series of manganese dioxide crystal formations, cryptomelane (KMn8O16, OMS-2, α-MnO2) and birnessite (OL-1, δ-MnO2) it is common structure。OMS-2 and OL-1 is MnO6The manganese and oxygen compound that octahedra chain structure is formed with different connection form, wherein forms 2 × 2 pore passage structures at OMS-2, then forms two dimension (2D) layer structure in OL-1。Due to the performance such as pore structure of they uniquenesses, mixed valence (3+, 4+), easily discharging [12] such as Lattice Oxygen, OMS-2 and OL-1 catalysis material has been widely used for the fields such as the useful chemical products of selective catalysis synthesis, catalytic oxidation organic pollution, water oxidation catalysis。Although MnO2Base catalysis material is cheap and easy to get, but many factors such as specific surface area, acid-base value, hydrophobicity and reducing power etc. affect its catalysis activity to a certain extent, how strengthening its catalysis activity and substituting the use of noble-metal-supported catalyst is the significant challenge faced at present。On the one hand, in cryptomelane (OMS-2) skeleton or duct, improve its catalysis activity by mixing transition metal and alkali metal, be subject to people and pay attention to。There are some researches show, when mixing the transition metals such as Mo, V, Cu and Fe in the skeleton of OMS-2, it is possible to cause its pattern to become hollow ball from nanometer rods, thus causing the increase of its specific surface area。When mixing alkali metal Li+ and Cs+ in the duct of OMS-2, by increasing capacitance it is possible to increase its surface basicity and strengthen its reducing power。But said method exists maximum problem, and to be that catalysis activity increase rate and latent active improve inconspicuous。On the other hand by reducing particle size, to increase surface area and control the method for pattern be also important means。But these method intrinsic reactivities improve also little。Stratiform birnessite OL-1 is few in catalysis VOCs application aspect research, has been reported that the catalysis activity of the OL-1 showing nanostructured depends on its pattern, particle size, surface area and catalyst surface reducing power at present。But compare pore passage structure OMS-2 catalysis material, the Research Literature being used for improving the methods and strategies of OL-1 catalysis activity is fewer, we are necessary the catalysis activity developing a kind of strategy to improve OL-1, so that stratiform birnessite OL-1 can substitute noble-metal-supported catalyst and use。Based on this, the present invention is from MnO2Unique physical and chemical performance sets out, for how to improve MnO2Catalyst based catalytic oxidation VOCs activity problems, at high activity MnO2The regulation and control of catalyst based micro structure, doping and catalytic purification aspect of performance have carried out further investigation, are desirably to obtain the catalytic capability that can compare favourably with noble-metal-supported catalyst。
Summary of the invention
It is an object of the invention to provide a kind of with low cost, controllability good, the Zn of high-cleanness quality2+Doping MnO2Catalyst based nanometer rods and synthetic method thereof。
A kind of Zn of the present invention2+Doping MnO2Catalyst based nanometer rods, diameter is 1～10 nanometer, and length is 10-200 nanometer, and crystal formation is α-MnO2。Pass through Zn2+There is the hydrothermal oxidization reduction reaction of gentleness at a certain temperature in solution and permanganate。Comprise the following steps: 1) by the Zn of 4.3422 units2+Compound is dissolved in a certain amount of distilled water, is then added rapidly in above-mentioned solution by the permanganate of 4.7412 units；2) stirring under magnetic stirrer, whipping temp is 90-120 DEG C, until permanganate is completely dissolved；3) above-mentioned solution is transferred to equipped with, in the stainless steel cauldron of the polytetrafluoroethylliner liner of 100mL, being heated to 100-200 DEG C under inert protective atmosphere, be incubated 1-36 hour；4) question response terminates, and is taken out by reactor and at room temperature cools down；5) by reacted product centrifugation, use distilled water cyclic washing, then dry under infrared lamp, obtain Zn2+Doping MnO2Catalyst based nanometer rods。
Zn of the present invention2+Compound is water-soluble zinc sulfate, zinc nitrate or zinc chloride etc.。
Permanganate of the present invention is high manganese lithium, sodium permanganate, potassium permanganate, ammonium permanganate, acerdol, Barium manganate(VII)., zinc permanganate, magnesium permanganate, permanganic acid hydrargyrum, cadmium permanganate, permanganic acid rubidium etc.。
Inert protective gas of the present invention is purity be more than 99% argon and nitrogen。
Accompanying drawing explanation
Fig. 1: a kind of Zn of the present invention2+Doping MnO2TEM and the HRTEM of catalyst based nanometer rods；
Fig. 2: XPS full spectrogram；
Fig. 3: N2 adsorption-desorption isothermal curve。
Detailed description of the invention
Once for adopting the inventive method synthesis Zn2+Doping MnO2The example of catalyst based nanometer rods, the present invention is not limited to these embodiments。
Embodiment 1
1) by the Zn (NO of 4.3422g3)2It is dissolved in the distilled water of 40ml, then by the KMnO of 4.7412g4It is added rapidly in above-mentioned solution；
2) stirring under magnetic stirrer, whipping temp is 90 DEG C, until permanganate is completely dissolved；
3) above-mentioned solution is transferred to equipped with, in the stainless steel cauldron of the polytetrafluoroethylliner liner of 100mL, being heated to 120 DEG C under the inert protective atmosphere of the argon that purity is more than 99% and nitrogen, be incubated 36 hours；
4) question response terminates, and is taken out by reactor and at room temperature cools down；
5) by reacted product centrifugation, use distilled water cyclic washing, then dry under infrared lamp, obtain Zn2+Doping MnO2Catalyst based nanometer rods。
The product obtained carrying out TEM Electronic Speculum take pictures (see Fig. 1), it can be seen that nanorod diameter is 10-20 nanometer, length is 10-100 nanometer。Product is carried out XPS test, and test result is shown in Fig. 2, and in nanometer rods, the signal of zinc element is very strong as we know from the figure, it was demonstrated that zinc element really adulterates and enters MnO2Catalyst based OMS-2 nanometer rods。As can be seen from Figure 3, this product has effective adsorption for VOC (VOCs), extensively arrives air purification field。
Embodiment 2
1) by the Zn (NO of 4.3422g3)2It is dissolved in the distilled water of 40ml, then by the MgMnO of 4.7412g4It is added rapidly in above-mentioned solution；
2) stirring under magnetic stirrer, whipping temp is 90 DEG C, until permanganate is completely dissolved；
3) above-mentioned solution is transferred to equipped with, in the stainless steel cauldron of the polytetrafluoroethylliner liner of 100mL, being heated to 160 DEG C under the inert protective atmosphere of the argon that purity is more than 99% and nitrogen, be incubated 36 hours；
4) question response terminates, and is taken out by reactor and at room temperature cools down；
5) by reacted product centrifugation, use distilled water cyclic washing, then dry under infrared lamp, obtain diameter 20-30 nanometer, the Zn of length 100-200 nanometer2+Doping MnO2Catalyst based nanometer rods。
Embodiment 3
1) by the Zn (NO of 4.3422g3)2It is dissolved in the distilled water of 40ml, then by the BaMnO of 5.1547g4It is added rapidly in above-mentioned solution；
2) stirring under magnetic stirrer, whipping temp is 90 DEG C, until permanganate is completely dissolved；
3) above-mentioned solution is transferred to equipped with, in the stainless steel cauldron of the polytetrafluoroethylliner liner of 100mL, being heated to 180 DEG C under the inert protective atmosphere of the argon that purity is more than 99% and nitrogen, be incubated 36 hours；
4) question response terminates, and is taken out by reactor and at room temperature cools down；
5) by reacted product centrifugation, use distilled water cyclic washing, then dry under infrared lamp, obtain diameter 10-20 nanometer, the Zn of length 50-200 nanometer2+Doping MnO2Catalyst based nanometer rods。
Claims (5)
1. a Zn2+Doping MnO2Catalyst based nanometer rods, it is characterised in that: this nanorod diameter is 1～10 nanometer, and length is 10-200 nanometer, and crystal formation is α-MnO2。
2. a Zn as claimed in claim 12+Doping MnO2The synthetic method of catalyst based nanometer rods, it is characterised in that: pass through Zn2+There is the hydrothermal oxidization reduction reaction of gentleness at a certain temperature in solution and permanganate。Comprise the following steps:
1) by the Zn of 4.3422 units2+Compound is dissolved in a certain amount of distilled water, is then added rapidly in above-mentioned solution by the permanganate of 4.7412 units；
2) stirring under magnetic stirrer, whipping temp is 90-120 DEG C, until permanganate is completely dissolved；
3) above-mentioned solution is transferred to equipped with, in the stainless steel cauldron of the polytetrafluoroethylliner liner of 100mL, being heated to 100-200 DEG C under inert protective atmosphere, be incubated 1-36 hour；
4) question response terminates, and is taken out by reactor and at room temperature cools down；
5) by reacted product centrifugation, use distilled water cyclic washing, then dry under infrared lamp, obtain Zn2+Doping MnO2Catalyst based nanometer rods。
3. Zn according to claim 22+Doping MnO2The synthetic method of catalyst based nanometer rods, it is characterised in that: described Zn2+Compound is water-soluble zinc sulfate, zinc nitrate or zinc chloride etc.。
4. Zn according to claim 22+Doping MnO2The synthetic method of catalyst based nanometer rods, it is characterised in that: described permanganate is high manganese lithium, sodium permanganate, potassium permanganate, ammonium permanganate, acerdol, Barium manganate(VII)., zinc permanganate, magnesium permanganate, permanganic acid hydrargyrum, cadmium permanganate, permanganic acid rubidium etc.。
5. Zn according to claim 22+Doping MnO2The synthetic method of catalyst based nanometer rods, it is characterised in that described inert protective gas is purity be more than 99% argon and nitrogen。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610003885.XA CN105692701B (en) | 2016-01-05 | 2016-01-05 | A kind of Zn2+Adulterate MnO2Base catalyst nano rod and its synthetic method |
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| CN201610003885.XA CN105692701B (en) | 2016-01-05 | 2016-01-05 | A kind of Zn2+Adulterate MnO2Base catalyst nano rod and its synthetic method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768262A (en) * | 2019-01-25 | 2019-05-17 | 天津理工大学 | A kind of cadmium modified manganese dioxide positive electrode and its preparation method and application |
| CN110102287A (en) * | 2018-02-01 | 2019-08-09 | 北京化工大学 | A kind of metal-doped modified layered δ-MnO2And its it prepares and applies |
| CN110227484A (en) * | 2019-07-16 | 2019-09-13 | 河北工业大学 | A kind of doped nano manganese dioxide composite material, preparation method and applications |
| CN110252334A (en) * | 2019-07-16 | 2019-09-20 | 河北工业大学 | A kind of doped nano manganese dioxide composite material, preparation method and applications |
| CN110655113A (en) * | 2019-09-29 | 2020-01-07 | 南昌大学 | Na-doped MnO2Preparation method of electrode material |
| CN115212870A (en) * | 2022-07-14 | 2022-10-21 | 西南交通大学 | Cesium-doped sodium type layered manganese dioxide VOCs catalyst and preparation method and application thereof |
| US11484621B2 (en) * | 2018-08-14 | 2022-11-01 | Purespace Inc. | Catalyst structure for ozone decomposition |
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Cited By (12)
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| CN110102287A (en) * | 2018-02-01 | 2019-08-09 | 北京化工大学 | A kind of metal-doped modified layered δ-MnO2And its it prepares and applies |
| CN110102287B (en) * | 2018-02-01 | 2021-06-22 | 北京化工大学 | Metal-doped modified layered delta-MnO2And their preparation and use |
| US11484621B2 (en) * | 2018-08-14 | 2022-11-01 | Purespace Inc. | Catalyst structure for ozone decomposition |
| CN109768262A (en) * | 2019-01-25 | 2019-05-17 | 天津理工大学 | A kind of cadmium modified manganese dioxide positive electrode and its preparation method and application |
| CN109768262B (en) * | 2019-01-25 | 2021-12-24 | 天津理工大学 | Cadmium modified manganese dioxide positive electrode material and preparation method and application thereof |
| CN110227484A (en) * | 2019-07-16 | 2019-09-13 | 河北工业大学 | A kind of doped nano manganese dioxide composite material, preparation method and applications |
| CN110252334A (en) * | 2019-07-16 | 2019-09-20 | 河北工业大学 | A kind of doped nano manganese dioxide composite material, preparation method and applications |
| CN110227484B (en) * | 2019-07-16 | 2023-11-28 | 河北工业大学 | Doped nano manganese dioxide composite material, preparation method and application thereof |
| CN110252334B (en) * | 2019-07-16 | 2023-12-19 | 河北工业大学 | Doped nano manganese dioxide composite material, preparation method and application thereof |
| CN110655113A (en) * | 2019-09-29 | 2020-01-07 | 南昌大学 | Na-doped MnO2Preparation method of electrode material |
| CN115212870A (en) * | 2022-07-14 | 2022-10-21 | 西南交通大学 | Cesium-doped sodium type layered manganese dioxide VOCs catalyst and preparation method and application thereof |
| CN115212870B (en) * | 2022-07-14 | 2023-09-01 | 西南交通大学 | Cesium doped sodium layered manganese dioxide VOCs catalyst and preparation method and application thereof |
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