CN109592715A - A method of using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide - Google Patents
A method of using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide Download PDFInfo
- Publication number
- CN109592715A CN109592715A CN201811568684.XA CN201811568684A CN109592715A CN 109592715 A CN109592715 A CN 109592715A CN 201811568684 A CN201811568684 A CN 201811568684A CN 109592715 A CN109592715 A CN 109592715A
- Authority
- CN
- China
- Prior art keywords
- manganese
- tpa
- terephthalic acid
- hydration
- presoma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of using two hydration terephthalic acid (TPA) manganese as the method for presoma controllable preparation different structure manganese oxide, this method is using two hydration terephthalic acid (TPA) manganese as presoma, select potassium permanganate as oxidant, using thermal method, by adjusting pH, temperature and the molar ratio of potassium permanganate and presoma, to obtain the manganese oxide of different types of structure.Preparation method of the present invention is simple, and reaction condition is mild, the abundant and stable cellular structure using complex, it can be achieved that various structures manganese oxide (such as: cryptomelane α-MnO2, pyrolusite β-MnO2, nsutite γ-MnO2, birnessite δ-MnO2, hausmannite) controllable preparation, be a kind of very promising preparation method.
Description
Technical field
The invention belongs to manganese oxide preparation technical fields, and in particular to a kind of using two hydration terephthalic acid (TPA) manganese as presoma
The method for preparing different structure manganese oxide by hydro-thermal method.
Background technique
Manganese oxide belongs to both sexes transition metal oxide, is deposited under room temperature with highly stable black or brown powder solid
?.The basic structural unit for constituting manganese oxide crystal is MnO6Octahedron, this octahedra 6 oxygen atom and octahedron by vertex
1 manganese atom at center is coordinated to be formed.Adjacent MnO6It connects to form a variety of knots in a manner of total rib or corner-sharing between octahedron
The manganese oxide crystal of structure.Although the basic structural unit for constituting manganese oxide crystal is identical, due to MnO6Octahedra connection type
Difference, manganese oxide crystal have various structures, such as: cryptomelane α-MnO2(2 × 2 tunnel type), pyrolusite β-MnO2(1 × 1 tunnel
Type), nsutite γ-MnO2(tunnel type of 1 × 1+2 × 1), birnessite δ-MnO2(stratiform, there are H for interlayer2O), hausmannite
(Mn3O4) etc..In recent years, aoxidize manganese material preparation method mainly have solution technique, solid-bed break-up method, hydrothermal/solvent thermal method,
Sol-gel method, microemulsion method, chemical precipitation method etc., chemical vapour deposition technique etc., but water is used by presoma of complex
The method that heat/solvent-thermal method prepares manganese oxide is not reported also.
Coordination polymer is due to, there are strong interaction, making its structure between metal ion or metal cluster and organic ligand
High stability, and there is unique space net structure, huge diameter distribution.Nowadays there are many using complex as presoma
Carbon/oxide correlative study of preparation, preparation method mostly use calcination method, it is forged under the action of the protective gas such as nitrogen
It burns, the elements such as hydrogen-oxygen leave complex material by gas form, and carbon skeleton remains, and are formed using carbon as the hole of skeleton.
Calcination method reacts more demanding temperature, may destroy original skeleton of complex, and reaction condition is single, product species
It is single.
Summary of the invention
The object of the present invention is to provide one kind to prepare difference by hydro-thermal method using two hydration terephthalic acid (TPA) manganese as presoma
The method of structure manganese oxide.
For above-mentioned purpose, the technical scheme adopted by the invention is that: by two hydration terephthalic acid (TPA) manganese and potassium permanganate
It is added in deionized water for 1:0.25~2.00 in molar ratio, and with sour or adjusting PH with base=1~13, in confined conditions 80~
120 DEG C are reacted 2~5 days, are cooled to room temperature, and obtained solid product is dry after 0.1mol/L NaOH solution centrifuge washing, are obtained
Manganese oxide；
It is in molar ratio that 1:0.5~2.00 add by two hydration terephthalic acid (TPA) manganese and potassium permanganate in above-mentioned preparation method
Enter in deionized water, and with acid or adjusting PH with base=3~11, in confined conditions 80~120 DEG C react 2~5 days, be cooled to often
Temperature, obtained solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains 2 × 2 tunnel type α-MnO2。
It is in molar ratio that 1:0.25~1.00 add by two hydration terephthalic acid (TPA) manganese and potassium permanganate in above-mentioned preparation method
Enter in deionized water, and with acid or adjusting PH with base=0.5~1, in confined conditions 110~120 DEG C react 2~5 days, be cooled to often
Temperature, obtained solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains 1 × 1 tunnel type β-MnO2。
It is in molar ratio that 1:0.25~0.50 adds by two hydration terephthalic acid (TPA) manganese and potassium permanganate in above-mentioned preparation method
Enter in deionized water, and with acid or adjusting PH with base=0.5~1, in confined conditions 80~100 DEG C react 2~5 days, be cooled to often
Temperature, obtained solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains the tunnel type γ of 1 × 1+2 × 1-MnO2。
It is in molar ratio that 1:0.50~2.00 add by two hydration terephthalic acid (TPA) manganese and potassium permanganate in above-mentioned preparation method
Enter in deionized water, and with acid or adjusting PH with base=12~13, in confined conditions 80~120 DEG C react 2~5 days, be cooled to often
Temperature, obtained solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains stratiform δ-MnO2。
It is in molar ratio that 1:0.25~0.35 adds by two hydration terephthalic acid (TPA) manganese and potassium permanganate in above-mentioned preparation method
Enter in deionized water, and with acid or adjusting PH with base=3~11, in confined conditions 85~120 DEG C react 2~5 days, be cooled to often
Temperature, obtained solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains Mn3O4。
The structural unit of above-mentioned two hydrations terephthalic acid (TPA) manganese is Mn (C8H4O4)(H2O)2, it is according to document
“Terephthalate salts of dipositive cations,Acta Crystallographica.(2002).B58,
Method disclosed in 815-822 " is prepared.
Above-mentioned acid is sulfuric acid, phosphoric acid, any one in acetic acid；Alkali is sodium hydroxide, potassium hydroxide, any one in ammonium hydroxide
Kind.
Beneficial effects of the present invention are as follows:
The present invention prepares manganese oxide by hydro-thermal method using two hydration terephthalic acid (TPA) manganese as presoma, abundant using presoma
And stable cellular structure makes the structure species of product manganese oxide have a possibility that more；The utilization of hydro-thermal method is so that reaction item
Part is milder, is conducive to the Mn in oxidant potassium permanganate in-situ oxidation precursor construction2+, and may be implemented to reaction item
The adjusting of part (pH, temperature etc.) regulates and controls the performance of product to effectively improve the type of product, is a kind of very promising
Preparation method.
Detailed description of the invention
Fig. 1 is the cryptomelane α-MnO of Examples 1 to 8 preparation2Powder x-ray diffraction figure.
Fig. 2 is cryptomelane α-MnO prepared by embodiment 72Flied emission electron microscope.
Fig. 3 is pyrolusite β-MnO prepared by embodiment 9 and 102Powder x-ray diffraction figure.
Fig. 4 is pyrolusite β-MnO prepared by embodiment 102Flied emission electron microscope.
Fig. 5 is nsutite γ-MnO prepared by embodiment 11 and 122Powder x-ray diffraction figure.
Fig. 6 is birnessite δ-MnO prepared by embodiment 13~162Powder x-ray diffraction figure.
Fig. 7 is hausmannite Mn prepared by embodiment 17~193O4Powder x-ray diffraction figure.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
0.025g (0.157mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=3 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 85 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2.By Fig. 1
It is found that the powder x-ray diffraction curve and standard PDF card of products therefrom coincide, illustrate that product is cryptomelane.
Embodiment 2
0.025g (0.157mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese, 10mL
Deionized water is added in the vial with polytetrafluoroethylene (PTFE) lid, is uniformly mixed, in confined conditions 85 DEG C of standing reactions
3.5 days, room temperature is naturally cooled to, pours out supernatant liquor, the solid product of bottom is washed with 0.1mol/L NaOH aqueous solution
After washing, being centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2(see Fig. 1).
Embodiment 3
0.050g (0.314mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=9 is added, is uniformly mixed, in closed item
The lower 85 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2(see figure
1)。
Embodiment 4
0.099g (0.628mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=11 is added, is uniformly mixed, closed
Under the conditions of 85 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, by the solid product 0.1mol/ of bottom
After L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2(see
Fig. 1).
Embodiment 5
0.099g (0.628mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=3 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 120 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2(see figure
1)。
Embodiment 6
0.025g (0.157mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=5 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 120 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2(see figure
1)。
Embodiment 7
0.050g (0.314mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese, 10mL
Deionized water is added in the vial with polytetrafluoroethylene (PTFE) lid, is uniformly mixed, in confined conditions 120 DEG C of standing reactions
3.5 days, room temperature is naturally cooled to, pours out supernatant liquor, the solid product of bottom is washed with 0.1mol/L NaOH aqueous solution
After washing, being centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-MnO2(see Fig. 1).It is sent out from field shown in Fig. 2
Penetrating electron microscope can be seen that its pattern is elongated rodlike.
Embodiment 8
0.050g (0.314mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=11 is added, is uniformly mixed, closed
Under the conditions of 120 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, the solid product of bottom is used
After 0.1mol/L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 2 × 2 tunnel type cryptomelane α-
MnO2(see Fig. 1).
Embodiment 9
0.0125g (0.079mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=1 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 120 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 1 × 1 tunnel type pyrolusite β-MnO2.By Fig. 3
It is found that the powder x-ray diffraction curve and standard PDF card of products therefrom coincide, illustrate that product is pyrolusite.
Embodiment 10
0.050g (0.314mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=1 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 120 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain 1 × 1 tunnel type pyrolusite β-MnO2(see figure
3).It can be seen that its pattern is irregular and approximate cuboid from Flied emission electron microscope shown in Fig. 4.
Embodiment 11
0.0125g (0.079mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=1 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 85 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain the tunnel type nsutite of 1 × 1+2 × 1 γ-
MnO2.As shown in Figure 5, the powder x-ray diffraction curve of products therefrom and standard PDF card coincide, and illustrate that product is six Fang Meng
Mine.
Embodiment 12
0.025g (0.157mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=1 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 85 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/ of bottom
After LNaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain the tunnel type nsutite of 1 × 1+2 × 1 γ-
MnO2(see Fig. 5).
Embodiment 13
0.025g (0.157mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=13 is added, is uniformly mixed, closed
Under the conditions of 85 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, by the solid product 0.1mol/ of bottom
After L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain stratiform birnessite δ-MnO2.It can by Fig. 6
Know, the powder x-ray diffraction curve and standard PDF card of products therefrom coincide, and illustrate that product is birnessite.
Embodiment 14
0.050g (0.314mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=13 is added, is uniformly mixed, closed
Under the conditions of 85 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, by the solid product 0.1mol/ of bottom
After L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain stratiform birnessite δ-MnO2(see Fig. 6).
Embodiment 15
0.025g (0.157mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=13 is added, is uniformly mixed, closed
Under the conditions of 120 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, the solid product of bottom is used
After 0.1mol/L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain stratiform birnessite δ-MnO2
(see Fig. 6).
Embodiment 16
0.099g (0.628mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=13 is added, is uniformly mixed, closed
Under the conditions of 120 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, the solid product of bottom is used
After 0.1mol/L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain stratiform birnessite δ-MnO2
(see Fig. 6).
Embodiment 17
0.0125g (0.079mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the H of 10mL pH=3 is added2SO4Aqueous solution is uniformly mixed, in closed item
The lower 85 DEG C of standings of part are reacted 3.5 days, are naturally cooled to room temperature, are poured out supernatant liquor, by the solid product 0.1mol/L of bottom
After NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain hausmannite Mn3O4.As shown in Figure 7, gained produces
The powder x-ray diffraction curve and standard PDF card of object coincide, and illustrate that product is hausmannite.
Embodiment 18
By 0.0125g (0.079mmol) potassium permanganate and 0.080g (0.314mmol) two be hydrated terephthalic acid (TPA) manganese,
10mL deionized water is added in the vial with polytetrafluoroethylene (PTFE) lid, is uniformly mixed, in confined conditions 85 DEG C of standings
Reaction 3.5 days, naturally cool to room temperature, pour out supernatant liquor, by the solid product of bottom with 0.1mol/L NaOH aqueous solution into
After row washing, centrifugation, dries at 60 DEG C to constant weight, obtain hausmannite Mn3O4(see Fig. 7).
Embodiment 19
0.0125g (0.079mmol) potassium permanganate and 0.080g (0.314mmol) two are hydrated terephthalic acid (TPA) manganese to be added
In vial with polytetrafluoroethylene (PTFE) lid, the NaOH aqueous solution of 10mL pH=11 is added, is uniformly mixed, closed
Under the conditions of 85 DEG C of standings react 3.5 days, naturally cool to room temperature, pour out supernatant liquor, by the solid product 0.1mol/ of bottom
After L NaOH aqueous solution is washed, is centrifuged, dries at 60 DEG C to constant weight, obtain hausmannite Mn3O4(see Fig. 7).
Claims (8)
1. a kind of using two hydration terephthalic acid (TPA) manganese as the method for presoma controllable preparation different structure manganese oxide, feature exists
In:
By two hydration terephthalic acid (TPA) manganese and potassium permanganate in molar ratio it is that 1:0.25~2.00 is added in deionized water, and with sour
Or adjusting PH with base=1~13, it reacts 2~5 days for 80~120 DEG C, is cooled to room temperature in confined conditions, obtained solid product warp
It is dry after 0.1mol/L NaOH solution centrifuge washing, obtain manganese oxide；
The structural unit of above-mentioned two hydrations terephthalic acid (TPA) manganese is Mn (C8H4O4)(H2O)2。
2. according to claim 1 using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide
Method, it is characterised in that: be hydrated terephthalic acid (TPA) manganese for two and potassium permanganate is that deionization is added in 1:0.5~2.00 in molar ratio
In water, and with acid or adjusting PH with base=3~11, in confined conditions 80~120 DEG C react 2~5 days, be cooled to room temperature, gained is solid
Body product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains 2 × 2 tunnel type α-MnO2。
3. according to claim 1 using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide
Method, it is characterised in that: by two hydration terephthalic acid (TPA) manganese and potassium permanganate be in molar ratio 1:0.25~1.00 addition go from
In sub- water, and with acid or adjusting PH with base=0.5~1, in confined conditions 110~120 DEG C react 2~5 days, be cooled to room temperature, institute
It is dry after 0.1mol/L NaOH solution centrifuge washing to obtain solid product, obtains 1 × 1 tunnel type β-MnO2。
4. according to claim 1 using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide
Method, it is characterised in that: by two hydration terephthalic acid (TPA) manganese and potassium permanganate be in molar ratio 1:0.25~0.50 addition go from
In sub- water, and with acid or adjusting PH with base=0.5~1, in confined conditions 80~100 DEG C react 2~5 days, be cooled to room temperature, gained
Solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains the tunnel type γ of 1 × 1+2 × 1-MnO2。
5. according to claim 1 using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide
Method, it is characterised in that: by two hydration terephthalic acid (TPA) manganese and potassium permanganate be in molar ratio 1:0.50~2.00 addition go from
In sub- water, and with acid or adjusting PH with base=12~13, in confined conditions 80~120 DEG C react 2~5 days, be cooled to room temperature, gained
Solid product is dry after 0.1mol/LNaOH solution centrifuge washing, obtains stratiform δ-MnO2。
6. according to claim 1 using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide
Method, it is characterised in that: by two hydration terephthalic acid (TPA) manganese and potassium permanganate be in molar ratio 1:0.25~0.35 addition go from
In sub- water, and with acid or adjusting PH with base=3~11, in confined conditions 85~120 DEG C react 2~5 days, be cooled to room temperature, gained
Solid product is dry after 0.1mol/L NaOH solution centrifuge washing, obtains Mn3O4。
7. different as presoma controllable preparation using two hydration terephthalic acid (TPA) manganese described in any one according to claim 1~6
The method of structure manganese oxide, it is characterised in that: the acid is sulfuric acid, phosphoric acid, any one in acetic acid.
8. different as presoma controllable preparation using two hydration terephthalic acid (TPA) manganese described in any one according to claim 1~6
The method of structure manganese oxide, it is characterised in that: the alkali is sodium hydroxide, potassium hydroxide, any one in ammonium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811568684.XA CN109592715B (en) | 2018-12-21 | 2018-12-21 | Method for controllably preparing manganese oxide with different structures by taking manganese terephthalate dihydrate as precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811568684.XA CN109592715B (en) | 2018-12-21 | 2018-12-21 | Method for controllably preparing manganese oxide with different structures by taking manganese terephthalate dihydrate as precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109592715A true CN109592715A (en) | 2019-04-09 |
| CN109592715B CN109592715B (en) | 2021-04-20 |
Family
ID=65963232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811568684.XA Expired - Fee Related CN109592715B (en) | 2018-12-21 | 2018-12-21 | Method for controllably preparing manganese oxide with different structures by taking manganese terephthalate dihydrate as precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109592715B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410232A (en) * | 2020-04-26 | 2020-07-14 | 张韩生 | Preparation method of manganese dioxide positive electrode material |
| CN112768713A (en) * | 2021-01-09 | 2021-05-07 | 南开大学 | Carbon-loaded delta-MnO for aluminum-air battery2Catalyst and preparation method of air electrode |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503813A (en) * | 2011-09-22 | 2012-06-20 | 曹善文 | Method for recovering organic acid and cobalt manganese metal in terephthalic acid oxidation residue |
| CN103165912A (en) * | 2013-02-28 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Catalytic agent for lithium-air battery cathode and preparation method |
| WO2015195179A2 (en) * | 2014-03-28 | 2015-12-23 | The Regents Of The University Of California | Metal organic frameworks comprising a plurality of sbus with different metal ions and/or a plurality of organic linking ligands with different functional groups. |
| CN105363416A (en) * | 2015-12-07 | 2016-03-02 | 中国科学院生态环境研究中心 | Manganese dioxide nanowire @ multidimensional mesoporous metal organic framework adsorbent and preparation method thereof |
| CN106345527A (en) * | 2016-09-30 | 2017-01-25 | 上海理工大学 | Mn base metal organic skeletal catalyst, and preparation method and application thereof in air pollution prevention |
| CN107032408A (en) * | 2017-04-26 | 2017-08-11 | 浙江大学 | A kind of ferroso-ferric oxide/C classifying nano spherical structure composites of MnO doping and preparation method thereof |
| US9943839B2 (en) * | 2014-07-15 | 2018-04-17 | Northwestern University | Catalyst composition and process for preparing olefin oxides |
-
2018
- 2018-12-21 CN CN201811568684.XA patent/CN109592715B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503813A (en) * | 2011-09-22 | 2012-06-20 | 曹善文 | Method for recovering organic acid and cobalt manganese metal in terephthalic acid oxidation residue |
| CN103165912A (en) * | 2013-02-28 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Catalytic agent for lithium-air battery cathode and preparation method |
| WO2015195179A2 (en) * | 2014-03-28 | 2015-12-23 | The Regents Of The University Of California | Metal organic frameworks comprising a plurality of sbus with different metal ions and/or a plurality of organic linking ligands with different functional groups. |
| US9943839B2 (en) * | 2014-07-15 | 2018-04-17 | Northwestern University | Catalyst composition and process for preparing olefin oxides |
| CN105363416A (en) * | 2015-12-07 | 2016-03-02 | 中国科学院生态环境研究中心 | Manganese dioxide nanowire @ multidimensional mesoporous metal organic framework adsorbent and preparation method thereof |
| CN106345527A (en) * | 2016-09-30 | 2017-01-25 | 上海理工大学 | Mn base metal organic skeletal catalyst, and preparation method and application thereof in air pollution prevention |
| CN107032408A (en) * | 2017-04-26 | 2017-08-11 | 浙江大学 | A kind of ferroso-ferric oxide/C classifying nano spherical structure composites of MnO doping and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410232A (en) * | 2020-04-26 | 2020-07-14 | 张韩生 | Preparation method of manganese dioxide positive electrode material |
| CN111410232B (en) * | 2020-04-26 | 2022-12-02 | 张韩生 | Preparation method of manganese dioxide positive electrode material |
| CN112768713A (en) * | 2021-01-09 | 2021-05-07 | 南开大学 | Carbon-loaded delta-MnO for aluminum-air battery2Catalyst and preparation method of air electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109592715B (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Fe incorporated α-Co (OH) 2 nanosheets with remarkably improved activity towards the oxygen evolution reaction | |
| Billy et al. | Dissolution mechanisms of LiNi1/3Mn1/3Co1/3O2 positive electrode material from lithium-ion batteries in acid solution | |
| Liu et al. | Layered oxide cathodes for sodium‐ion batteries: From air stability, interface chemistry to phase transition | |
| Zhang et al. | Regulating the electronic structure of manganese-based materials to optimize the performance of zinc-ion batteries | |
| Xu et al. | Storage mechanisms and improved strategies for manganese-based aqueous zinc-ion batteries | |
| CN109592715A (en) | A method of using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide | |
| Mei et al. | Nano polymorphism‐enabled redox electrodes for rechargeable batteries | |
| Dong et al. | Self-supporting 1T-MoS2@ WS2@ CC composite materials for potential high-capacity sodium storage system | |
| CN110508308B (en) | Preparation method and application of CoMn-P-NCNT multifunctional catalyst | |
| Cheng et al. | Metal organic frameworks derived active functional groups decorated manganese monoxide for aqueous zinc ion battery | |
| CN103170646A (en) | Synthetic method of nanometer materials of cobalt fractal structure | |
| CN107946554A (en) | A kind of preparation method of lithium battery lithium titanate anode material | |
| Miyamoto et al. | Synthesis of ultrasmall Li–Mn spinel oxides exhibiting unusual ion exchange, electrochemical and catalytic properties | |
| Feng et al. | Facile design and synthesis of Co-free layered O3-type NaNi0. 2Mn0. 2Fe0. 6O2 as promising cathode material for sodium-ion batteries | |
| Gond et al. | Na 2 MnP 2 O 7 polymorphs as efficient bifunctional catalysts for oxygen reduction and oxygen evolution reactions | |
| Zhang et al. | P-doping Li2CoSiO4/C cathode material: A joint experimental and theoretical study | |
| Xu et al. | Nanostructured amorphous manganese oxide cryogel as a high-rate lithium intercalation host | |
| CN103928654B (en) | A kind of vanadic acid copper nano particles and preparation method thereof | |
| CN104835956A (en) | Method of preparing lithium ion battery anode material from two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like | |
| CN105197999B (en) | A kind of Hemicentrotus seu Strongylocentrotus dendroid γ-MnO2preparation method and electro-catalysis application | |
| Huynh et al. | One-Step Hydrothermal Synthesis of a New Nanostructure Ti0 7Ir0 3O2 for Enhanced Electrical Conductivity: The Effect of pH on the Formation of Nanostructure | |
| CN109244415A (en) | A kind of preparation method of spherical shape carbon coating titanate composite negative pole material | |
| Zhao et al. | Synthesis of Integrated Layered‐Spinel Composite Cathode Materials for High‐Voltage Lithium‐Ion Batteries up to 5.0 V | |
| CN104971751A (en) | Magnetic alpha-Fe2O<3-[delta]>C<[delta]>/FeVO<4-x+[delta]>C<x-[delta]> heterojunction photocatalyst, preparation method and applications thereof | |
| CN108557902B (en) | A kind of CoFe2O4The preparation method and applications of quantum dot |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210420 Termination date: 20211221 |