CN108002443A - MnO for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst and application - Google Patents

MnO for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst and application Download PDF

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CN108002443A
CN108002443A CN201711260230.1A CN201711260230A CN108002443A CN 108002443 A CN108002443 A CN 108002443A CN 201711260230 A CN201711260230 A CN 201711260230A CN 108002443 A CN108002443 A CN 108002443A
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catalyst
mno
sewage
mineralising
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CN108002443B (en
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朱永法
杨文娟
尤飞
闫龙
马亚军
卢翠英
马向荣
高平强
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Tsinghua University
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of MnO with normal pressure depth mineralising phenolic waste water ability2The preparation method of catalyst, belongs to thermocatalytic field of material technology.Potassium permanganate is mixed with reduction adjuvant first, obtains suspension, by suspension when 180 250 degrees Celsius of reactions 10 15 are small, after natural cooling, you can obtain the MnO of depth mineralization ability2Catalyst.MnO prepared by the method for the present invention2Catalyst, has the excellent activity of depth mineralising phenol wastewater, and the preparation method of the present invention, its raw material is cheap, and method is simple, therefore effectively reduces product cost, has the great value of environmental protection, has very high practical value and application prospect.

Description

MnO for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst and application
Technical field
The present invention relates to a kind of MnO for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst and application, belong to In thermocatalytic field of material technology.
Background technology
Phenol wastewater is one of industrial wastewater that world today's harm is big, pollution range is wide.Therefore, how rationally and effectively Phenol-Containing Wastewater Treatment is the important problem of environmental protection.The method of Phenol-Containing Wastewater Treatment includes materialization treatment process, biochemical treatment process And method of chemical treatment.Wherein in method of chemical treatment, the catalyst research applied to the wet oxidation process under high temperature and pressure is more, Much industrialize.And the catalytic oxidation technologies under normal temperature and pressure are also immature, corresponding catalyst report is also relatively fewer.
In catalytic oxidant under existing normal temperature and pressure, manganese dioxide is because of its special physicochemical properties, such as hole Road structure, catalytic property, redox property and it is widely present, it is cheap to be easy to get, it is environmental-friendly and be subject to people extensive Concern.Manganese dioxide has α-MnO2,β-MnO2,γ-MnO2,δ-MnO2,λ-MnO2,η-MnO2,ε-MnO2Deng various structures.Its In, cryptomelane (KMn8O16, OMS-2, α-MnO2) and birnessite (OL-1, δ-MnO2) it is common structure.OMS-2 by 2 × 2 pore passage structures form, and are made of in OL-1 two-dimensional layered structure.Due to their unique pore structures, mixed valence (3+, 4 +), the easy release performance such as Lattice Oxygen, the material such as OMS-2 and OL-1 be widely used to selective catalysis synthesis chemical products, The fields such as catalysis oxidation organic pollution, water oxidation catalysis.MnO is improved at present2The method of material catalytic performance includes:Reduction Particle size or increase specific surface area, containing transition metal and alkali metal, prepare the MnO of different-shape2, prepare different crystal forms MnO2。
CN101891297A obtains manganese dioxide nano-rod by easy hydro-thermal method, adds it to and gives up containing phenol In the ozonization water treatment system of water, promote the degraded of phenol organic pollution.CN105645474B with farina and Potassium permanganate (KMnO4) it is starting material, hexagon manganese dioxide (MnO is made by hydro-thermal reaction2) nanometer sheet material. CN104409219B is reported using manganese nitrate as manganese source, and low-crystalline layer can be directly obtained by simple redox reaction Shape manganese dioxide.Low-crystalline stratiform manganese oxide hydro-thermal process in sodium hydroxide solution, you can obtain high crystalline δ type dioxies Change manganese nano wire bundle.
The content of the invention
The object of the present invention is to provide a kind of MnO for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst It is higher to equipment requirement for the problem that the complex process in prior art with application, to MnO2The preparation process of catalyst into Row improves, and with process simplification, reduces production cost.This method has been directly obtained using simple immersion method has High Efficiency Thermal It is catalyzed the catalyst of phenol wastewater activity.
MnO proposed by the present invention for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst, including following step Suddenly：
(1) potassium permanganate and reduction adjuvant are mixed, the mass ratio of mixing is：Potassium permanganate: reduction adjuvant=1: (0.1-0.6), adds deionized water 70mL-100mL, the mass-volume concentration for making mixture is 5.0- in the mixture 10.769g/L, obtains suspension, and the reduction adjuvant is manganese sulfate monohydrate or Diammonium oxalate monohydrate；
(2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, it is Celsius in 80-200 When the lower reaction 12 of degree is small, after being cooled to room temperature solution, it is centrifuged, consolidating of being centrifugally separating to obtain is washed with deionized Body；
(3) solid of above-mentioned steps (3) is heated to 90-120 degrees Celsius, when insulation 20-30 is small, is obtained after natural cooling MnO with normal pressure depth mineralising phenolic waste water ability2Catalyst.
Manganese dioxide-catalyst prepared by the method for the present invention, can be applied to sewage disposal, application process includes following step Suddenly：
(1) in 50mL, 2,4- phenol concentrations are to add manganese dioxide-catalyst in the sewage of 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in manganese dioxide-catalyst；
(3) sewage of above-mentioned steps (2) is heated under such as 30 degrees Celsius, 60 degrees Celsius of different temperatures, the time reaches for sewage It is limited to discharge standard.
MnO proposed by the present invention for normal-temperature deep mineralising phenolic waste water2Its is excellent for the preparation method of catalyst and application Putting is：
1st, manganese dioxide-catalyst prepared by the method for the present invention, compound with regular structure, crystallinity is high, therefore possesses more excellent urge Change performance.Using the oxygen defect on the surface of manganese dioxide, make manganese dioxide-catalyst that there is very high application value.And urge Change has the characteristics that safe and environment-friendly, efficient, makes the application prospect of the manganese dioxide-catalyst prepared of the invention boundless.
2nd, for the method for the present invention by simple hydro-thermal, water-bath technique, is prepared for manganese dioxide-catalyst, and preparation method It is easy to operate, it is cheap using raw material, it is easy to repeat, solves the problems such as cumbersome preparing for catalyst, low output, should for commercialization With providing good technical foundation and material guarantee.
3rd, manganese dioxide-catalyst prepared by the method for the present invention, just there is remarkable depth mineralising to contain phenol at room temperature, at a normal Physical performance is polluted, by the active group on paramagnetic spectrogram detection manganese dioxide-catalyst surface, it was found that peroxide, super oxygen and hydroxyl Base free radical group, and as temperature raises, the concentration of peroxy radical gradually increases, and peroxyl species have stronger oxidation Property, for the chief active group of phenol catalytic degradation.At room temperature for the degradation of organic pollution, therefore for environment Pollutant has regulation effect；Therefore there is extensive use in fields such as sewage disposals, there is very high practical value and application Prospect.
Brief description of the drawings
Fig. 1 is that (001) MnO is prepared in embodiment 12(100) MnO2The X-ray diffraction spectrogram of catalyst.
Fig. 2 is that (001) MnO is prepared in embodiment 12The electron scanning micrograph of catalyst.
Fig. 3 is that (001) MnO is prepared in embodiment 12The transmission electron microscope photo of catalyst.
Fig. 4 is that (001) MnO is prepared in embodiment 12The high resolution transmission electron microscopy photo of catalyst.
Fig. 5 is that (100) MnO is prepared in embodiment 32The electron scanning micrograph of catalyst.
Fig. 6 is that (100) MnO is prepared in embodiment 32The high resolution transmission electron microscopy photo of catalyst.
Fig. 7 is that (100) MnO is prepared in embodiment 32The high resolution transmission electron microscopy photo of catalyst.
Fig. 8 is (100) MnO in embodiment 42The Kinetics Rate Constants By Using (k) of catalyst degradation of phenol at different temperatures Comparison diagram.
Fig. 9 is (100) MnO in embodiment 42Catalyst at different temperatures, degrade 2,4- Dichlorophenols kinetic rate Constant (k) comparison diagram.
Figure 10 is (100) MnO in embodiment 42Degree of degradation of the catalyst in room temperature degradation of phenol
Figure 11 is (100) MnO in embodiment 42Velocity constant of the catalyst in room temperature degradation of phenol.
Figure 12 is (100) MnO in embodiment 42Intermediate product of the catalyst in room temperature degradation of phenol.
Figure 13 is (100) MnO in embodiment 42Schematic diagram of the catalyst in the salinity of room temperature degradation of phenol.
Embodiment
MnO proposed by the present invention for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst, including following step Suddenly：
(1) potassium permanganate and reduction adjuvant are mixed, the mass ratio of mixing is：Potassium permanganate: reduction adjuvant=1: (0.1-0.6), adds deionized water 70mL-100mL, the mass-volume concentration for making mixture is 5.0- in the mixture 10.769g/L, obtains suspension, and the reduction adjuvant is manganese sulfate monohydrate or Diammonium oxalate monohydrate；
(2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, it is Celsius in 80-200 When the lower reaction 12 of degree is small, after being cooled to room temperature solution, it is centrifuged, consolidating of being centrifugally separating to obtain is washed with deionized Body；
(3) solid of above-mentioned steps (3) is heated to 90-120 degrees Celsius, when insulation 20-30 is small, is obtained after natural cooling MnO with normal pressure depth mineralising phenolic waste water ability2Catalyst.
Above-mentioned MnO2Catalyst, can be applied to phenol sewage disposal, comprise the following steps：
(1) manganese dioxide-catalyst, the addition of manganese dioxide-catalyst are added in the phenol sewage that organic contamination produces Mass volume ratio is 0.5~5g/L；
(2) it is sufficiently stirred, manganese dioxide-catalyst is uniformly dispersed in sewage；
(3) sewage of above-mentioned steps (2) is heated in the case where different temperatures is from 30 degrees Celsius to 80 degrees Celsius, the time reaches for sewage It is limited to discharge standard.
The embodiment of the present invention introduced below, material, reagent used in following embodiments etc., unless otherwise specified, It is commercially available.
Used in the following embodiments of the present invention is that potassium permanganate and the commercially available analysis of oxammite are pure, target degraded Pollutant phenol and 2,4-DCP are that commercially available analysis is pure, and pure water is self-control.
Embodiment 1：
(1) 1.0g potassium permanganate and 0.15g manganese sulfate monohydrates are mixed, adds 70mL deionized waters thereto, hanged Turbid；
(2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, at 200 degrees Celsius When lower reaction 12 is small, after being cooled to room temperature solution, it is centrifuged, consolidating of being centrifugally separating to obtain is washed with deionized Body；
(3) solid of above-mentioned steps (2) is heated to 105 degrees Celsius, when insulation 24 is small, obtains having after natural cooling normal Press 001 crystal face MnO of depth mineralising phenolic waste water ability2Catalyst.
The MnO prepared using U.S. Rigaku D/max-2400 type X-ray diffractometers testing example 12The crystalline substance of catalyst Body structure is XRD spectrum as shown in Figure 1.From spectrogram as can be seen that MnO2Crystallinity be not very good, at 12.3 °, 24.6 °, 36.5 ° and 65.5 ° of peak and birnessite MnO2(001) of (JCPDS No.80-1098), (002), (100) and (110) phase Matching.Fig. 2 is (001) MnO2Sample, show nanometer sheet composition nanometer flower structure；High-resolution transmission electricity shown in Fig. 3 In sub- microphotograph, (001) MnO2Show nanometer sheet packed structures；High resolution transmission electron microscopy shown in Fig. 4 shines In piece, it is observed that the crystallization situation of material, it was demonstrated that exposed crystal face is 001 crystal face.
Embodiment 2：
(1) 1.0g potassium permanganate and 0.3g manganese sulfate monohydrates are mixed, adds 100mL deionized waters thereto, hanged Turbid；
(2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, at 200 degrees Celsius When lower reaction 15 is small, after being cooled to room temperature solution, it is centrifuged, consolidating of being centrifugally separating to obtain is washed with deionized Body；
(3) solid of above-mentioned steps (2) is heated to 100 degrees Celsius, when insulation 30 is small, obtains having after natural cooling normal Press 001 crystal face MnO of depth mineralising phenolic waste water ability2Catalyst.
Embodiment 3：
(1) 1.0 potassium permanganate and the Diammonium oxalate monohydrate of 0.4g are weighed, 130mL deionized waters is added thereto, is hanged Turbid；
(2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, will be obtained outstanding Turbid in water-bath at 90 DEG C stirring reaction 12 it is small when, after being cooled to room temperature solution, be centrifuged, use deionized water Wash the solid being centrifugally separating to obtain；
(3) solid of above-mentioned steps (2) is heated to 105 DEG C, when insulation 24 is small, is obtained after natural cooling deep with normal pressure Spend the MnO of 100 crystal faces of mineralising phenolic waste water depth mineralization ability2Catalyst.
Fig. 5 is (100) MnO2Sample, show a nanometer spherical structure；High resolution transmission electron microscopy shown in Fig. 6 shines In piece, (100) MnO2Show a nanometer spherical structure；In high resolution transmission electron microscopy photo shown in Fig. 7, it is observed that The crystallization situation of material, it was demonstrated that exposed crystal face is 100 crystal faces.
Embodiment 4：
(1) 2.0 potassium permanganate and the Diammonium oxalate monohydrate of 0.4g are weighed, 150mL deionized waters is added thereto, is hanged Turbid；
(2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, will be obtained outstanding Turbid in water-bath at 90 DEG C stirring reaction 20 it is small when, after being cooled to room temperature solution, be centrifuged, use deionized water Wash the solid being centrifugally separating to obtain；
(3) solid of above-mentioned steps (2) is heated to 90 DEG C, when insulation 30 is small, is obtained after natural cooling deep with normal pressure Spend the MnO2 catalyst of 100 crystal faces of mineralising phenolic waste water depth mineralization ability.
Embodiment 5：
Catalyst is used for catalytic degradation phenol sewage, comprises the following steps：
Using phenol as target contaminant, to the MnO of the preparation of embodiment 12The ability of the degradation of phenol of catalyst sample, that is, urge Change activity to be studied.
(1) in 50mL, 25mg manganese dioxide-catalysts are added in the sewage that bisphenol A concentration is 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in manganese dioxide-catalyst；
(3) sewage of above-mentioned steps (2) is heated in the case where different temperatures is from 30 degrees Celsius to 80 degrees Celsius, the time reaches for sewage It is limited to discharge standard.
As can be seen from Fig. 8, phenol is used to be investigated for target-probe molecule to its activity.Fig. 8 is MnO2Catalyst The apparent reaction rate constant figure in different temperatures degradation of phenol (5ppm).It can be seen from the figure that catalyst MnO2System Just there is the performance of degradation of phenol at 30 degree, and improve the enhancing that temperature is conducive to degradation property.
Embodiment 6：
MnO2The catalysis of catalyst is used for Dichlorophenol sewage of degrading, and comprises the following steps：
Using colourless phenyl pollutant as target contaminant, to the MnO of the preparation of embodiment 12Catalyst sample is in different temperatures Under degradation capability studied, its activity is investigated for target-probe molecule using 2,4- Dichlorophenols.
(1) in 50mL, 2,4- Dichlorophenols concentration is to add manganese dioxide-catalyst in the sewage of 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in manganese dioxide-catalyst；
(3) sewage of above-mentioned steps (2) is heated under such as 30 degrees Celsius, 60 degrees Celsius of different temperatures, the time reaches for sewage It is limited to discharge standard.
Fig. 9 is MnO2The apparent reaction rate constant in different temperatures degraded 2,4- dichloros phenol solution (5ppm) of catalyst Figure.It can be seen from the figure that catalyst MnO2System just has the performance of degraded 2,4- Dichlorophenols at 30 degree, and raising temperature has Beneficial to the enhancing of degradation property.
Embodiment 7：
MnO2Catalyst is used for room temperature catalytic degradation phenol sewage, comprises the following steps：
(1) in 50mL, 25mg manganese dioxide-catalysts are added in the sewage that bisphenol A concentration is 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in manganese dioxide-catalyst；
(3) reach discharge standard in the sewage of room temperature reaction above-mentioned steps (2), time for sewage and be limited.
Figure 10 is that embodiment 1 prepares (100) MnO2The degree of degradation of catalyst, at room temperature degradation of phenol, Figure 11 are real Apply (100) MnO of the preparation of example 12The velocity constant of catalyst, at room temperature degradation of phenol, Figure 12 are prepared by embodiment 1 (100)MnO2The intermediate product of catalyst, at room temperature degradation of phenol, Figure 13 are that embodiment 1 prepares (100) MnO2Catalyst, The salinity of degradation of phenol at room temperature.It can be seen from the figure that catalyst room temperature can mineralising phenol, and intermediate product compared with It is few, change over time at room temperature, at a normal with remarkable depth mineralising containing phenol pollution physical performance.

Claims (2)

  1. A kind of 1. MnO for normal-temperature deep mineralising phenolic waste water2The preparation method of catalyst, the preparation method include following step Suddenly：
    (1) potassium permanganate and reduction adjuvant are mixed, the mass ratio of mixing is：Potassium permanganate: reduction adjuvant=1: (0.1- 0.6) deionized water 70mL-100mL, is added in the mixture, the mass-volume concentration for making mixture is 5.0-10.769g/L, Suspension is obtained, the reduction adjuvant is manganese sulfate monohydrate or Diammonium oxalate monohydrate；
    (2) suspension of above-mentioned steps (1) is placed in hydro-thermal reaction container or water-bath container, under 80-200 degrees Celsius React 10-15 it is small when, after being cooled to room temperature solution, be centrifuged, consolidating of being centrifugally separating to obtain be washed with deionized Body；
    (3) solid of above-mentioned steps (2) is heated to 90-120 degrees Celsius, when insulation 20-30 is small, is had after natural cooling The MnO of normal pressure depth mineralising phenolic waste water ability2Catalyst.
  2. A kind of 2. MnO as claimed in claim 12The application of catalyst, it is characterised in that be applied to manganese dioxide-catalyst Phenol sewage disposal, comprises the following steps：
    (1) manganese dioxide-catalyst, the addition matter of manganese dioxide-catalyst are added in the sewage (phenol) that organic contamination produces Amount volume ratio is 0.5~5g/L；
    (2) it is sufficiently stirred, manganese dioxide-catalyst is uniformly dispersed in sewage；
    (3) sewage of above-mentioned steps (2) is heated in the case where different temperatures is from 30 degrees Celsius to 80 degrees Celsius, the time reaches row for sewage The standard of putting is limited.
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CN116253364A (en) * 2023-01-30 2023-06-13 昆明理工大学 Application of birnessite type manganese dioxide in low-temperature catalytic decomposition of methyl mercaptan

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CN112654594A (en) * 2018-09-07 2021-04-13 国立大学法人东京工业大学 Method for producing oxide using beta-manganese dioxide
CN109250801A (en) * 2018-10-24 2019-01-22 大连理工大学 A kind of processing method of phenolic waste water
CN111514887A (en) * 2020-04-28 2020-08-11 重庆工商大学 α -MnO with exposed specific crystal face2Alpha crystal form metal oxide catalyst and preparation method thereof
CN111686679A (en) * 2020-06-01 2020-09-22 山西大学 Preparation method and application of manganese dioxide aerogel material
CN113368849A (en) * 2021-07-02 2021-09-10 河北华清环境科技集团股份有限公司 Preparation method and application of polygonal manganese dioxide nanosheet catalytic material
CN114832832A (en) * 2022-06-06 2022-08-02 武汉理工大学 Copper doped alpha-MnO 2 -110 catalyst, preparation method and application thereof
CN115957621A (en) * 2023-01-30 2023-04-14 昆明理工大学 Application of manganese oxide in catalytic decomposition of mixed mercaptan
CN116253364A (en) * 2023-01-30 2023-06-13 昆明理工大学 Application of birnessite type manganese dioxide in low-temperature catalytic decomposition of methyl mercaptan

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