CN108706596A - Doping type multi wall adulterates the preparation method of the oxygen murmanite nanotube of vanadium - Google Patents

Doping type multi wall adulterates the preparation method of the oxygen murmanite nanotube of vanadium Download PDF

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CN108706596A
CN108706596A CN201810531098.1A CN201810531098A CN108706596A CN 108706596 A CN108706596 A CN 108706596A CN 201810531098 A CN201810531098 A CN 201810531098A CN 108706596 A CN108706596 A CN 108706596A
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nanotube
doping type
murmanite
oxygen
preparation
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董国君
徐芳芳
严永轶
骈珊
张欣
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Harbin Engineering University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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Abstract

The present invention is to provide the preparation methods that a kind of doping type multi wall adulterates the oxygen murmanite nanotube of vanadium.One, titanyl sulfate and ammonium metavanadate are dissolved in the aqueous solution of oxalic acid；Two, the aqueous solution of sodium metasilicate is added in the solution obtained to step 1, is precipitated, mechanical agitation；Three, by step 2 product be aged, washing filters, and dry, roasting obtains composite powder；Four, sodium hydroxide solution is put into reaction kettle, adds composite powder and cationic surfactant after mixing, hydro-thermal reaction；Five, the product after hydro-thermal uses nitric acid treatment after suction filtration, then washes and centrifuges, obtains solid content；Six, the solid content drying, roasting obtains doping type V-Na2TiOSiO4Many walls nanotube.Gained nanotube specific surface area of the invention is up to 316m2/ g, uniform at pipe, nanometer pipe range has three layers or double-layer tube wall up to 1~2 μm.

Description

Doping type multi wall adulterates the preparation method of the oxygen murmanite nanotube of vanadium
Technical field
The present invention relates to a kind of preparation method of nanotube, specifically a kind of V-Na2TiOSiO4Nanotube Preparation method.
Background technology
Tubular nanometer material in absorption, separation, ion exchange and is urged because of its larger specific surface area and unique pore structure The fields such as change have a wide range of applications.Hydro-thermal method, template and electrochemical method have become the main method for preparing nanotube, Wherein hydro-thermal method is most widely used.Titania nanotube (Li, R.M. are prepared using hydro-thermal method；Chen,G.M.；Dong, G.J.,et al.Controllable synthesis of nanostructured TiO2by CTAB-assisted Hydrothermal route.New Journal of Chemistry, 2014,10,4684-4689.) it is more mature skill Art.Oxygen murmanite (Natisite) is a kind of widely used heat-resisting material, more in the existing years of researches history of foreign countries The powder of kind structure oxygen murmanite has all successfully prepared, and also has many articles to report in terms of element doping.Such as exist Vanadium (Ismail, N. are adulterated in ETS-4 and natisite；Abd El-Maksod,I.H.；Ezzat,H.Synthesis and characterization of titanosilicates from white sand silica and its hydrogen Uptake.International Journal of Hydrogen Energy, 2010,19,10359-10365.) obtained oxygen Murmanite powder, the doping of V element is to increasing material structure defect, improving surface acidity bit quantity, raising catalytic performance all Beneficial contribution.The doping of V element is that V element is successfully introduced intracell and improves material instead of Ti elements Performance.The present inventor is successfully prepared Na early period2(TiO)SiO4Double-walled nanotubes (Zhong, Y.；Chang,S.； Dong,G.Preparation and characterization of a novel double-walled Na2(TiO) SiO4nanotube by hydrothermal process with CTAB as an assistant.Microporous and Mesoporous Materials,2017,239,70-77；Patent of invention 201510271068.8 prepares double-walled Na2 (TiO)SiO4The method of nanotube), to improve the performance of such nano-tube material, carry out various research work.
Invention content
It is uniform at pipe that the purpose of the present invention is to provide a kind of, and doping type multi wall easy to operate adulterates the oxygen silicon titanium sodium of vanadium The preparation method of stone nanotube.
The object of the present invention is achieved like this：
The ammonium metavanadate of titanyl sulfate 5~9g and 0.01~0.2g are dissolved in the aqueous solution of 0.04g oxalic acid by step 1；
Step 2 in the solution obtained to step 1, is added 50% aqueous solution that 4~12g sodium metasilicate is prepared, controls silicic acid The addition rate of sodium is 80~200mL/min, is precipitated, mechanical agitation 2h；
Step 3, by step 2 product be aged 10h at 50 DEG C, washing filters, until in filtrate sulfate radical-free from Son detects, and is dried at 100 DEG C, roasts 5h at 300~400 DEG C, obtains composite powder；
The sodium hydroxide solution of 9~15mol/L is put into reaction kettle by step 4, add composite powder described in 1~5g and The cationic surfactant of 0.2~1g after mixing, 20~32h of hydro-thermal reaction at 150~220 DEG C；
Step 5, product after hydro-thermal is after suction filtration with the nitric acid treatment less than 1.0mol/L at a temperature of 25~80 DEG C Then 0.5~1h washes and centrifuges 3min under 4000~6000r/min rates, obtains solid content；
Step 6, the solid content dry 4~8h at 100 DEG C, roast 3~6h at 300~500 DEG C, obtain doping type V-Na2TiOSiO4Many walls nanotube.
Na2(TiO)SiO4English name be：natisite；Chinese translation is：Oxygen murmanite.The V- of the present invention Na2TiOSiO4It is named as：Adulterate the oxygen murmanite of vanadium.
The present invention can also include：
1, the ammonium metavanadate of titanyl sulfate 5~9g and 0.01~0.2g are dissolved in the aqueous solution of 0.04g oxalic acid in step 1 In after, the mechanical agitation 1h at 40 DEG C.
2, the mechanical agitation in step 2, control speed of agitator are 50~80r/min.
3, the cationic surfactant is CTAB or DTAB.
The present invention prepares doping type multi wall using the strongly basic medium hydro-thermal stripping composite powder method of surfactant auxiliary V-Na2TiOSiO4Nanotube.Gained nanotube specific surface area is up to 316m2/ g, it is uniform at pipe, nanometer pipe range up to 1~2 μm, With three layers or double-layer tube wall.
The present invention uses new raw material, and V is obtained in the way of controllable double hydrolysis2O5-TiO2-SiO2Composite powder uses Conventional hydrothermal method prepares doping type V-Na2TiOSiO4Many walls nanotube.Three-layer pipe wall nanometer pipe outer wall and interior wall thickness are 0.45nm, middle wall thickness are 0.36nm, bore 4.89nm, pipe outside diameter 9.05nm；Double-layer tube wall pipe outer wall is 0.45nm, wall Spacing is 0.63nm, and wall internal diameter is 5.43nm, and wall outer diameter is 7.96nm, and specific surface area is up to 316m2/g.With high at pipe rate, The good advantage of pattern.And preparation method is easy to operate, low in raw material price.
Description of the drawings
Fig. 1 a~Fig. 1 c are the multi wall V-Na prepared in embodiment 12TiOSiO4Nanotube TEM (Fig. 1 a), SEM (Fig. 1 b), HRTEM (Fig. 1 c) figure.
Fig. 2 is the multi wall V-Na prepared in embodiment 22TiOSiO4Nanotube TEM figures.
Fig. 3 is the multi wall V-Na prepared in embodiment 32TiOSiO4Nanotube TEM figures.
Fig. 4 is the multi wall V-Na prepared in embodiment 42TiOSiO4Nanotube TEM figures.
Fig. 5 is the multi wall V-Na prepared in embodiment 52TiOSiO4Nanotube TEM figures.
Fig. 6 is multi wall V-Na prepared by the present invention2TiOSiO4The XRD diagram of nanotube, wherein Examples 1 to 5 correspond to respectively Sample S1~S5.
The table of Fig. 7 is multi wall V-Na prepared by the present invention2TiOSiO4The ICP of nanotube schemes, and wherein Examples 1 to 5 is distinguished Counter sample S1~S5.
Specific implementation mode
The doping type multi wall V-Na of the present invention2TiOSiO4The preparation method of nanotube includes the following steps：
Step 1, the ammonium metavanadate for weighing titanyl sulfate 5~9g and 0.01~0.2g are dissolved in prior dissolving 0.04g oxalic acid In deionized water, mechanical agitation 1h at 40 DEG C forms solution.
Step 2, according to (Ti+V):Si=1:The ratio of 1 (mol/mol) is slowly added to 4~12g silicon into above-mentioned solution 50% aqueous solution that sour sodium is prepared, it is 80~200mL/min that rate, which is added, in control, is precipitated, mechanical agitation 2h.Control rotating speed For 50~80r/min, V/Ti=0.02~10%.
Above-mentioned mixed liquor is aged 10h by step 3 at 50 DEG C, and washing filters, until sulfate radical-free ion is examined in filtrate Go out, is dried at 100 DEG C, roasts 5h at 300~400 DEG C, obtain the powder of composite powder.
The sodium hydroxide solution of 9~15mol/L is put into reaction kettle by step 4, add 1~5g composite powder and The cationic surfactant (CTAB or DTAB) of 0.2~1g after mixing, at 150~220 DEG C hydro-thermal reaction 20~ 32h。
Step 5, product after hydro-thermal is after suction filtration with the nitric acid treatment less than 1.0mol/L at a temperature of 25~80 DEG C Then 0.5~1h, auxiliary are washed with strong stirring and centrifuge 3min under 4000~6000r/min rates, obtained solid content.
Step 6, solids obtained above dry 4~8h at 100 DEG C, roast 3~6h at 300~500 DEG C, obtain Doping type V-Na2TiOSiO4Many walls nanotube.
Illustrating below, it is more detailed to be carried out to the effect of the present invention.
Embodiment 1：Multi wall V-Na2TiOSiO4The method and step of nanotube is as follows：
Step 1, the ammonium metavanadate for weighing 7.1g titanyl sulfates and 0.04g is dissolved in the deionization for dissolving 0.04g oxalic acid in advance In water, 1h forms solution.
Step 2,50% aqueous solution that 7g sodium metasilicate is prepared is added in above-mentioned solution, it is 120mL/min that rate, which is added, in control, It is precipitated, mechanical agitation 2h.Control rotating speed is 80r/min.
Step 3, above-mentioned mixed liquor is aged 10h at 50 DEG C, washing filters, until sulfate radical-free ion is examined in filtrate Go out, is dried at 100 DEG C, roasts 5h at 300 DEG C, obtain the powder of composite powder.
Step 4, it takes the sodium hydroxide solution of 32mL, 12mol/L to be put into reaction kettle, adds the composite powder and 0.5g of 2g Cationic surfactant after mixing, hydro-thermal reaction is for 24 hours at 180 DEG C.
Step 5, at the product after hydro-thermal at a temperature of 80 DEG C carries out acid with the nitric acid of a concentration of 0.3mol/L after suction filtration 0.5h is managed, then auxiliary is washed with strong stirring and centrifuges 3min under 4000r/min rates, obtained solid content.
Step 6, solids obtained above dries 8h at 100 DEG C, roasts 5h at 300 DEG C, obtains doping type V- Na2TiOSiO4Many walls nanotube.
Fig. 1 a, Fig. 1 b and Fig. 1 c are respectively the V-Na prepared according to embodiment 12TiOSiO4SEM, TEM of many walls nanotube Figure and HRTEM figures, nanotube is up to 1~2 μm, and at pipe rate about 100%, tube wall is smooth, and multi-layer wall is high-visible, after tested BET is 316m2/g。
Embodiment 2：Multi wall V-Na2TiOSiO4The method of nanotube, it is same as Example 1, the difference is that step 1, The ammonium metavanadate for weighing 7.1g titanyl sulfates and 0.1g is dissolved in the deionized water of dissolving 0.04g oxalic acid in advance, is stirred 1h, is formed Solution.
Fig. 2 is the V-Na prepared according to embodiment 22TiOSiO4Many walls nanotube TEM figures, multi wall is received as we can see from the figure Nanotube structures, pipe range be not high at tube efficiency between 10~100nm.
Embodiment 3：Multi wall V-Na2TiOSiO4The method of nanotube, it is same as Example 1, the difference is that step 2, 50% aqueous solution that 7g sodium metasilicate is prepared is added in above-mentioned solution, it is 60mL/min that rate, which is added, in control, is precipitated, machinery stirs Mix 2h.Control rotating speed is 80r/min.
Fig. 3 is the V-Na prepared according to embodiment 32TiOSiO4The TEM of many walls nanotube schemes, as we can see from the figure equal shape At nano tube structure, but pipe range is shorter, only about 200nm, and nanotube bending situation occurs.
Embodiment 4：Multi wall V-Na2TiOSiO4The method of nanotube, it is same as Example 1, the difference is that step 4, The sodium hydroxide solution of 32mL, 12mol/L is taken to be put into reaction kettle, the cationic surface of the composite powder and 0.5g that add 2g is lived After mixing, at 230 DEG C hydro-thermal reaction is for 24 hours for property agent.
Fig. 4 is the V-Na prepared according to embodiment 42TiOSiO4The TEM of many walls nanotube schemes, as we can see from the figure nanometer The length of pipe is uneven, more in the pipe of 40~400nm, the fragment of pipe occurs.
Embodiment 5：Multi wall V-Na2TiOSiO4The method of nanotube, it is same as Example 1, the difference is that step 4, The sodium hydroxide solution of 32mL, 12mol/L is taken to be put into reaction kettle, the cationic surface of the composite powder and 0.5g that add 2g is lived Property agent after mixing, the hydro-thermal reaction 34h at 180 DEG C.
Fig. 5 is the V-Na prepared according to embodiment 52TiOSiO4The TEM of many walls nanotube schemes, as we can see from the figure nanometer Nanotube pattern, it is preferable at pipe rate, but tube wall is relatively rough, it is multi wall structure that cannot be clearly seen.
Fig. 6 is V-Na prepared by five embodiments2TiOSiO4The XRD spectrum of many walls nanotube, be respectively designated as S1, S2, S3, S4 and S5.By vanadium doping V-Na2TiOSiO4The XRD diffraction maximums and standard card of material
The table 1 of Fig. 7 is multi wall V-Na prepared by five embodiments2TiOSiO4The ICP of nanotube schemes, wherein Examples 1 to 5 Counter sample S1~S5 respectively.

Claims (5)

1. a kind of preparation method of oxygen murmanite nanotube that mixing doping type multi wall doping vanadium, it is characterized in that：
The ammonium metavanadate of titanyl sulfate 5~9g and 0.01~0.2g are dissolved in the aqueous solution of 0.04g oxalic acid by step 1；
Step 2 in the solution obtained to step 1, is added 50% aqueous solution that 4~12g sodium metasilicate is prepared, controls sodium metasilicate Addition rate is 80~200mL/min, is precipitated, mechanical agitation 2h；
Step 3, by step 2 product be aged 10h at 50 DEG C, washing filters, until sulfate radical-free ion is examined in filtrate Go out, is dried at 100 DEG C, roasts 5h at 300~400 DEG C, obtain composite powder；
The sodium hydroxide solution of 9~15mol/L is put into reaction kettle, adds composite powder described in 1~5g and 0.2 by step 4 The cationic surfactant of~1g after mixing, 20~32h of hydro-thermal reaction at 150~220 DEG C；
Step 5, product after hydro-thermal after suction filtration at a temperature of 25~80 DEG C with the nitric acid treatment 0.5 less than 1.0mol/L~ Then 1h washes and centrifuges 3min under 4000~6000r/min rates, obtains solid content；
Step 6, the solid content dry 4~8h at 100 DEG C, roast 3~6h at 300~500 DEG C, obtain doping type V- Na2TiOSiO4Many walls nanotube.
2. the preparation method of the oxygen murmanite nanotube of doping type multi wall doping vanadium according to claim 1, feature It is：After the ammonium metavanadate of titanyl sulfate 5~9g and 0.01~0.2g are dissolved in the aqueous solution of 0.04g oxalic acid in step 1, The mechanical agitation 1h at 40 DEG C.
3. the preparation method of the oxygen murmanite nanotube of doping type multi wall doping vanadium according to claim 1 or 2, special Sign is：Mechanical agitation in step 2, control speed of agitator are 50~80r/min.
4. the preparation method of the oxygen murmanite nanotube of doping type multi wall doping vanadium according to claim 1 or 2, special Sign is：The cationic surfactant is CTAB or DTAB.
5. the preparation method of the oxygen murmanite nanotube of doping type multi wall doping vanadium according to claim 3, feature It is：The cationic surfactant is CTAB or DTAB.
CN201810531098.1A 2018-04-28 2018-05-29 Doping type multi wall adulterates the preparation method of the oxygen murmanite nanotube of vanadium Pending CN108706596A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103769188A (en) * 2013-12-26 2014-05-07 华北电力大学（保定） Three-atom-doped titanium dioxide as well as preparation method and application thereof
CN104986777A (en) * 2015-05-25 2015-10-21 哈尔滨工程大学 Method for preparation of double-wall Na2(TiO)SiO4 nanotube

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103769188A (en) * 2013-12-26 2014-05-07 华北电力大学（保定） Three-atom-doped titanium dioxide as well as preparation method and application thereof
CN104986777A (en) * 2015-05-25 2015-10-21 哈尔滨工程大学 Method for preparation of double-wall Na2(TiO)SiO4 nanotube

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GOW-WENG PENG ET AL.: ""FT-IR and XRD characterization of phase transformation of heat-treated synthetic natisite (Na2TiOSiO4) powder"", 《MATERIALS CHEMISTRY AND PHYSICS》 *
N. ISMAIL ET AL.: ""Synthesis and characterization of titanosilicates from white sand silica and its hydrogen uptake"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
YUKE ZHONG ET AL.: ""Preparation and characterization of a novel double-walled Na2(TiO) SiO4 nanotube by hydrothermal process with CTAB as an assistant"", 《MICROPOROUS AND MESOPOROUS MATERIALS》 *

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Application publication date: 20181026