CN104258845A - Amorphous manganese oxide and preparation method thereof - Google Patents
Amorphous manganese oxide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an amorphous manganese oxide and a preparation method thereof. The amorphous manganese oxide is an octahedral layered material of K-doped manganese oxide, wherein the molar ratio of K to Mn is (0.11-0.33):1.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to the doping of a kind of potassium element, can the amorphous Mn oxide that low concentration nitric oxide be removed under room temperature and preparation method thereof.
Background technology
Amorphous Mn oxide is synthesized by Steven L.Suib seminar reported first, is applied to afterwards in the oxidation of isopropyl alcohol, the light auxiliary catalysis oxidation of ethanol and the oxidation reaction of halogenated hydrocarbons and water due to the oxidation susceptibility of its excellence.Catalytic inner Lattice Oxygen deviate from ability and unnecessary Surface Oxygen causes material to have high catalytic performance.Unbodied Mn oxide normally utilizes potassium permanganate and reducing agent (such as Mn
2+, oxalic acid and fumaric acid) between simple redox reaction synthesis obtain.Octahedron molecular screen (OMS-2) and octahedra stratified material (OL-1) to two kinds of structures of amorphous Mn oxide most study.All containing K in these two kinds of structures
+and hydrone, difference is K in octahedron molecular screen
+be positioned at by MnO with hydrone
6the inside of the passage that octahedron surrounds, and in octahedra stratified material, K
+be positioned at by MnO with hydrone
6the interlayer of the layer of octahedra composition.
The nitrous oxides concentration that in hemi-closure space, (mainly roads and tunnels and underground parking) produces due to motor vehicle exhaust emission is lower, is about several ppm.For room-temperature catalytic oxidation mainly active carbon, zeolite and the transition metal oxide of NO, but above-mentioned material is mainly for the NO (higher than hundreds of ppm) of high concentration, and for the absorption of the NO of several ppm and the research of room temperature catalytic oxidation little.And the effect that the manganese oxide reported before is removed for the normal temperature of low concentration nitric oxide is undesirable, and catalysqt deactivation is serious in the presence of water.Therefore need room temperature badly remove the long-acting catalyst of low concentration of NO and require that catalyst has good water-resistance.
Summary of the invention
The present invention is intended to overcome the defect of existing manganese oxide at aspect of performance, the invention provides amorphous manganese oxide of a kind of potassium element doping and preparation method thereof.
The invention provides the amorphous Mn oxide of a kind of potassium element doping, described amorphous Mn oxide is the octahedra stratified material of Mn oxide of doping K, and the mol ratio between K and Mn is (0.11-0.33): 1.
Preferably, the aperture of described amorphous Mn oxide is 3.4-7.9, preferred 3.4-5.7nm, and specific area is 114-252m
2/ g.
Preferably, when room temperature, nitric oxide Nong Du≤10ppm, described amorphous Mn oxide is as nitric oxide production remover, and NO clearance 100% can maintain 10h, and NO clearance more than 50% can maintain 22h; When humidity in air be 50%, nitric oxide Nong Du≤10ppm time, described amorphous Mn oxide is as nitric oxide production remover, and NO clearance reaches 90%, reaches 168 hours effective time.
The invention provides a kind of preparation method of above-mentioned amorphous Mn oxide, described method comprises:
1) preparation contains the mixed solution of potassium permanganate and reducing agent, and wherein, the mol ratio between potassium permanganate and reducing agent is 1:(1-2);
2) at 25-40 DEG C, described mixed solution is made to react 8-48 hour under agitation;
3) by step 2) the complete mixed solution of middle reaction carries out suction filtration, washing obtains dark gum, and dry described dark gum, obtains described amorphous oxide.
Preferably, step 1) in, reducing agent comprises oxalic acid, glucose and/or citric acid.
Preferably, step 1) in, the manner of formulation of mixed solution is: be added dropwise in reductant solution by liquor potassic permanganate, or be added dropwise in liquor potassic permanganate by reductant solution.
Preferably, step 2) in, step 1) in, the mol ratio between potassium permanganate and reducing agent is 1:(1-2), preferred 1:(1-1.5).
Preferably, step 2) in, in the process of reaction, apply ultrasonic to mixed liquor.
Preferably, step 3) in, drying is carried out at 80-150 DEG C.
Beneficial effect of the present invention:
Contrast with the redox reaction of the potassium permanganate reported in document before and reducing agent (as oxalic acid), the present invention has following characteristics:
A. the mol ratio of potassium permanganate and oxalic acid is (1:1) ~ (1:2), and in document, be (1:2) ~ (1:2.5) (H.Cao, S.L.Suib, Journal of the American Chemical Society 116 (1994) 5334-5342.);
B. the reaction time longer (8-48h), and in document, be only 2h;
C. in the product obtained in the present invention, the mol ratio of K/Mn is about 0.3 (see table 2), and the mol ratio of K/Mn is 0.06 in the product reported in document, therefore in the present invention the K+ content of Mn oxide apparently higher than bibliographical information, this is the cause that ratio reduces and the reaction time extends due to oxalic acid, thus causes K+ content to increase and catalytic reaction for NO below has fabulous effect;
The Mn oxide specific area of the excellent catalytic effect prepared according to above technological process can reach 165m
2/ g, the clearance 100% of its room temperature low concentration of NO maintains 10h, and more than 50% maintains 22h.When humidity is 50%, the clearance more than 90% of NO maintains 168h.
Accompanying drawing explanation
Fig. 1 shows the XRD diffraction pattern of the Mn oxide synthesized under differential responses condition in the several embodiment of the present invention;
Fig. 2 shows the SEM photo of the Mn oxide synthesized under differential responses condition in the several embodiment of the present invention;
Fig. 3 shows TEM figure, HR-TEM figure and the electron diffraction diagram of the Mn oxide prepared in an embodiment of the invention;
Fig. 4 shows Mn oxide that in several embodiment of the present invention, differential responses condition obtains and removes performance test for normal temperature low concentration of NO, and test condition is: NO concentration is 10ppm, O
2content is 21%, and carrier gas is N
2, air speed is 120,000mL g
-1h
-1, reaction temperature is 25 DEG C;
Fig. 5 to show in an embodiment of the invention under humidity is 50% condition Mn oxide and removes performance test curve as catalyst for normal temperature low concentration nitric oxide.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention provides a kind of method that room temperature prepares amorphous Mn oxide, and use it for the catalytic oxidation of room temperature low concentration nitric oxide.The method is with potassium permanganate and oxalic acid for reaction raw materials, and at room temperature preparation has the mesoporous Mn oxide of high-specific surface area, homogeneous pore-size distribution.By regulating reactant ratio, reaction time, reaction temperature and dropping order, this unbodied Mn oxide can be obtained.The Mn oxide of the method synthesis has significant effect for the removal of normal temperature low concentration nitric oxide in the hemi-closure space of the city such as roads and tunnels, underground parking.In addition, this catalyst in the air with certain humidity, removal effect better (clearance of nitric oxide 90% can reach 168h).The method belongs to catalysis material technical field.
The technical scheme that room temperature prepares amorphous Mn oxide is as follows:
(1) liquor potassic permanganate is dropwise joined oxalic acid (as reducing agent)) in solution, form brownish black mixed liquor, stir;
(2) by said mixture suction filtration, product is obtained at 80 ~ 150 DEG C of temperature range inner dryings;
(3), in step (1), the mol ratio of potassium permanganate and oxalic acid is (1:1) ~ (1:2);
(4), in step (1), the reaction time is at 8h ~ 48h;
(5), in step (1), reaction temperature is 25 ~ 40 DEG C;
(6), in step (1), in course of reaction, the dropping order of potassium permanganate and oxalic acid can change;
(7), in step (1), reducing agent is not limited in oxalic acid, and glucose, citric acid etc. are all passable;
(8), in step (1), can add ultrasonic in course of reaction;
(9) above-mentioned gained powder is used for the catalytic oxidation of low concentration of NO, test condition is: NO concentration is 10ppm, O
2content is 21%, and carrier gas is N
2, air speed is 120,000mLg
-1h
-1, reaction temperature is 25 DEG C;
(10) above-mentioned gained powder is used for having the normal temperature of certain humidity to remove the method for low concentration nitric oxide, it is characterized in that: described contains O in oxygen NOx waste gas
2content be about 21%, NO content be about 10ppm, high humidity is about 30%-80%.
Reducing agent is not limited in oxalic acid, and glucose, citric acid etc. are all passable.
Baking temperature is within the scope of 80 ~ 150 DEG C.
Contrast with the redox reaction of the potassium permanganate reported in document before and oxalic acid, the present invention has following characteristics:
A. the mol ratio of potassium permanganate and oxalic acid is (1:1) ~ (1:2), and in document, be (1:2) ~ (1:2.5) (H.Cao, S.L.Suib, Journal of the American Chemical Society 116 (1994) 5334-5342.);
B. the reaction time longer (8-48h), and in document, be only 2h;
C. in the product obtained in the present invention, the mol ratio of K/Mn is about 0.3 (see table 2), and in the product reported in document, the mol ratio of K/Mn is 0.06, therefore the K of Mn oxide in the present invention
+content is apparently higher than bibliographical information, and this is the cause that ratio reduces and the reaction time extends due to oxalic acid, thus causes K
+content increases and catalytic reaction for NO below has fabulous effect.
The best Mn oxide specific area of the catalytic effect prepared according to above technological process is 165m
2/ g, the clearance 100% of its room temperature low concentration of NO maintains 10h, and more than 50% maintains 22h.When humidity is 50%, the clearance more than 90% of NO maintains 168h.
Feature of the present invention is:
(1) the method room temperature adopting redox to prepare synthesizes amorphous Mn oxide.By changing reaction condition, all product can be obtained;
(2) simply, cost is low, easy to utilize for equipment and manufacture craft;
(3) Mn oxide of the method synthesis is obvious for the removal effect of room temperature low concentration of NO, and 100% clearance maintains 10h, and more than 50% maintains 22h.And catalyst has good water-resistance, when humidity is 50%, the clearance more than 90% of NO maintains 168h.
Fig. 1 shows the XRD diffraction pattern of the Mn oxide synthesized under differential responses condition in the several embodiment of the present invention;
Fig. 2 shows the SEM photo of the Mn oxide synthesized under differential responses condition in the several embodiment of the present invention,
Wherein, in (a), the synthesis condition of product is that liquor potassic permanganate is added drop-wise in oxalic acid solution, reaction 24h, reaction temperature 25 DEG C, and the mol ratio of potassium permanganate and oxalic acid is 1:1.5;
The synthesis condition of product for a change (a) middle dropping order in (b), adopt oxalic acid solution to be added drop-wise in liquor potassic permanganate, other condition is constant;
C in (), the synthesis condition of product is, only change the mol ratio of potassium permanganate in (a) and oxalic acid into 1:1, other condition is constant;
D in (), the synthesis condition of product is, only change the mol ratio of potassium permanganate in (a) and oxalic acid into 1:2, other condition is constant;
E in (), the synthesis condition of product is, only change the reaction time in (a) into 8h, other condition is constant;
F in (), the synthesis condition of product is, only change the reaction time in (a) into 20h, other condition is constant;
G in (), the synthesis condition of product is, only change the reaction time in (a) into 28h, other condition is constant;
H in (), the synthesis condition of product is, only change the reaction time in (a) into 48h, other condition is constant;
I in (), the synthesis condition of product is, only change reaction temperature in (a) into 40 DEG C, other condition is constant;
Fig. 3 shows TEM figure, HR-TEM figure and the electron diffraction diagram of the Mn oxide prepared in an embodiment of the invention;
Fig. 4 shows Mn oxide that in several embodiment of the present invention, differential responses condition obtains and removes performance test for normal temperature low concentration of NO, and test condition is: NO concentration is 10ppm, O
2content is 21%, and carrier gas is N
2, air speed is 120,000mL g
-1h
-1, reaction temperature is 25 DEG C, wherein,
Mn oxide obtained under a condition in Mn representative graph 2 carries out test curve;
Mn oxide obtained under b condition in Mn-trans representative graph 2 carries out test curve;
Mn oxide obtained under c condition in Mn-1 representative graph 2 carries out test curve;
Mn oxide obtained under d condition in Mn-2 representative graph 2 carries out test curve;
Mn oxide obtained under e condition in Mn-8h representative graph 2 carries out test curve;
Mn oxide obtained under f condition in Mn-20h representative graph 2 carries out test curve;
Mn oxide obtained under g condition in Mn-28h representative graph 2 carries out test curve;
Mn oxide obtained under h in Mn-48h representative graph 2 carries out test curve;
Mn oxide obtained under i condition in Mn-40 DEG C of representative graph 2 carries out test curve;
Mn is best to the removal effect of NO, and the clearance of 100% can maintain 10h, and the clearance of 50% can maintain 22h; Secondly, the clearance of 50% is about 15h to the removal effect of Mn-trans, Mn-40 DEG C and Mn-28h.And Mn-48h and Mn-1 does not have effect completely;
Fig. 5 to show in an embodiment of the invention under humidity is 50% condition Mn oxide and removes performance test curve as catalyst for normal temperature low concentration nitric oxide.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following technological parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
Described in technical scheme and technological process.Be dissolved in by 1.58g potassium permanganate in 60mL deionized water, 1.89g bis-oxalic acid hydrate is dissolved in 100mL deionized water, is dropwise joined in oxalic acid solution by liquor potassic permanganate, stirring at room temperature 24h; By mixture suction filtration, washing, then the dark gum 120 DEG C of dried overnight obtained are obtained product.The XRD diffraction pattern of prepared Mn oxide is as shown in the curve being denoted as Mn in accompanying drawing 1, and its surface topography is as shown in (a) in accompanying drawing 2, and transmission electron microscope photo is shown in accompanying drawing 3.Its specific area is in table 1.The aperture of amorphous Mn oxide is 4.2nm;
As shown in Figure 5, adopt the Mn oxide of the present embodiment as catalyst, when humidity is 50%, the clearance more than 90% of NO maintains 168h.
Embodiment 2
Reaction time in embodiment 1 is adjusted to 8h, and all the other conditions are all consistent with embodiment 1, and prepared material (Mn-8h) is shown in Mn-8h curve in Fig. 4 for the performance test that removes of normal temperature low concentration of NO.The aperture of amorphous Mn oxide is 3.7nm.
Embodiment 3
Change the dropping order in embodiment 1 into oxalic acid solution dropwise to join in liquor potassic permanganate, all the other conditions are all consistent with embodiment 1, and prepared material (Mn-trans) is shown in Mn-trans in Fig. 4 for the performance test that removes of normal temperature low concentration of NO.The aperture of amorphous Mn oxide is 4.1nm.
Embodiment 4
Change the reaction temperature in embodiment 1 into 40 DEG C, all the other conditions are all consistent with embodiment 1, and prepared material (Mn-40 DEG C) is shown in Fig. 4 for the performance test that removes of normal temperature low concentration of NO.The aperture of amorphous Mn oxide is 3.6nm.
Embodiment 5
By mixed liquor in embodiment 1 as ultrasonic middle reaction 6h, all the other conditions are all consistent with embodiment 1.The aperture of amorphous Mn oxide (Mn-ultra) is 5.2nm.
Embodiment 6
Embodiment 1 mesoxalic acid is changed into the glucose of 0.05g, all the other conditions are all consistent with embodiment 1.The aperture of amorphous Mn oxide (Mn-glucose) is 7.9nm.
The specific area parameter of the Mn oxide that table 1. differential responses condition obtains
| Sample | Specific area | Aperture | Pore volume |
| ? | (m 2/g) | (nm) | (cm 3/g) |
| Mn | 166 | 4.2 | 0.18 |
| Mn-trans | 217 | 4.1 | 0.25 |
| Mn-1 | 135 | 4.6 | 0.17 |
| Mn-2 | 252 | 5.7 | 0.46 |
| Mn-8h | 114 | 3.7 | 0.11 |
| Mn-20h | 147 | 3.4 | 0.13 |
| Mn-28h | 156 | 3.4 | 0.15 |
| Mn-48h | 141 | 4.6 | 0.20 |
| Mn-40℃ | 165 | 3.6 | 0.17 |
| Mn-ultra | 175 | 5.2 | 0.41 |
| Mn-glucose | 185 | 7.9 | 0.58 |
Table 2 differential responses condition obtains the mol ratio of the K/Mn of product
| Sample | ICP-AES | EDX |
| Mn | 0.307 | 0.34 |
| Mn-trans | 0.309 | 0.26 |
| Mn-1 | 0.336 | 0.33 |
| Mn-2 | 0.111 | 0.12 |
| Mn-8h | 0.323 | 0.49 |
| Mn-20h | 0.324 | 0.38 |
| Mn-28h | 0.324 | 0.34 |
| Mn-48h | 0.329 | 0.30 |
| Mn-40℃ | 0.298 | 0.26 |
| Mn-ultra | 0.342 | 0.32 |
| Mn-glucose | 0.351 | 0.33 |
Claims (9)
1. an amorphous Mn oxide for potassium element doping, is characterized in that, described amorphous Mn oxide is the octahedra stratified material of Mn oxide of doping K, and the mol ratio between K and Mn is (0.11-0.33): 1.
2. amorphous Mn oxide according to claim 1, is characterized in that, the aperture of described amorphous Mn oxide is 3.4-7.9nm, preferred 3.4-5.7 nm, and specific area is 114-252m
2/ g.
3. amorphous Mn oxide according to claim 1 or 2, it is characterized in that, when room temperature, nitric oxide Nong Du≤10ppm, described amorphous Mn oxide is as nitric oxide production remover, NO clearance 100% can maintain 10 h, and NO clearance more than 50% can maintain 22 h; When humidity in air be 50%, nitric oxide Nong Du≤10ppm time, described amorphous Mn oxide is as nitric oxide production remover, and NO clearance reaches 90%, reaches 168 hours effective time.
4. the preparation method of arbitrary described amorphous Mn oxide in claim 1-3, it is characterized in that, described method comprises:
1) preparation contains the mixed solution of potassium permanganate and reducing agent, and wherein, the mol ratio between potassium permanganate and reducing agent is 1:(1-2);
2) at 25-40 DEG C, described mixed solution is made to react 8-48 hour under agitation;
3) by step 2) the complete mixed solution of middle reaction carries out suction filtration, washing obtains dark gum, and dry described dark gum, obtains described amorphous oxide.
5. preparation method according to claim 4, is characterized in that, in step 1), reducing agent comprises oxalic acid, glucose and/or citric acid.
6. the preparation method according to claim 4 or 5, is characterized in that, in step 1), the manner of formulation of mixed solution is: be added dropwise in reductant solution by liquor potassic permanganate, or be added dropwise in liquor potassic permanganate by reductant solution.
7. according to described preparation method arbitrary in claim 4-6, it is characterized in that, in step 1), the mol ratio between potassium permanganate and reducing agent is 1:(1-2).
8., according to described preparation method arbitrary in claim 4-7, it is characterized in that, step 2) in, in the process of reaction, apply ultrasonic to mixed liquor.
9. according to described preparation method arbitrary in claim 4-8, it is characterized in that, in step 3), drying is carried out at 80-150 DEG C.
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Cited By (8)
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|---|---|---|---|---|
| CN105327697A (en) * | 2015-11-18 | 2016-02-17 | 中国科学院上海硅酸盐研究所 | Method for preparing manganese dioxide catalyst for normal-temperature low-concentration NO catalytic purification with ultrasonic assisted alcohol-water solution method |
| CN106517345A (en) * | 2016-11-15 | 2017-03-22 | 南昌专腾科技有限公司 | Method for preparing superfine manganese dioxide by using potassium permanganate and potassium manganate |
| CN107754788A (en) * | 2017-11-02 | 2018-03-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Catalyst of formaldehyde catalytic degradation and its preparation method and application under normal temperature |
| CN108160070A (en) * | 2017-12-20 | 2018-06-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of amorphous manganese oxide of potassium ion doping and products thereof and application |
| CN108421524A (en) * | 2018-03-27 | 2018-08-21 | 天津大学 | A kind of carried non-crystal Mn oxide, preparation method and the usage |
| CN108479688A (en) * | 2018-03-27 | 2018-09-04 | 天津大学 | A kind of nano lamellar manganite adsorbent, preparation method and the usage |
| CN108744953A (en) * | 2018-05-22 | 2018-11-06 | 中南大学 | A kind of application process of OMS-2 and/or metal-doped OMS-2 catalysis denitrating flue gas |
| CN114534683A (en) * | 2022-02-14 | 2022-05-27 | 华侨大学 | Core-shell type magnetic nano material and preparation method and application thereof |
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| CN106517345A (en) * | 2016-11-15 | 2017-03-22 | 南昌专腾科技有限公司 | Method for preparing superfine manganese dioxide by using potassium permanganate and potassium manganate |
| CN106517345B (en) * | 2016-11-15 | 2018-01-05 | 南昌专腾科技有限公司 | Method for preparing ultrafine manganese dioxide by using potassium permanganate and potassium manganate |
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| CN108421524A (en) * | 2018-03-27 | 2018-08-21 | 天津大学 | A kind of carried non-crystal Mn oxide, preparation method and the usage |
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| CN108744953A (en) * | 2018-05-22 | 2018-11-06 | 中南大学 | A kind of application process of OMS-2 and/or metal-doped OMS-2 catalysis denitrating flue gas |
| CN108744953B (en) * | 2018-05-22 | 2020-06-30 | 中南大学 | Application method of OMS-2 and/or metal-doped OMS-2 catalytic flue gas denitration |
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