CN103864031A - Method for preparing nano-material with high specific surface area and pore volume - Google Patents
Method for preparing nano-material with high specific surface area and pore volume Download PDFInfo
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- CN103864031A CN103864031A CN201410120722.0A CN201410120722A CN103864031A CN 103864031 A CN103864031 A CN 103864031A CN 201410120722 A CN201410120722 A CN 201410120722A CN 103864031 A CN103864031 A CN 103864031A
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Abstract
The invention relates to a method for preparing a nano-material with high specific surface area and pore volume. According to the method, firstly, titania nanotubes, which have microcosmic morphologies and hierarchical structures similar to those of a cellulosic material, are prepared through taking the natural cellulosic material as a template and taking tetrabutyl titanate as a titanium precursor, and then a TiN nano-material with a three-dimensional communicated pore passage structure is prepared in a high-temperature (1,100-1,300 DEG C) tubular furnace by a magnesium thermal reduction method through taking magnesium metal as a reductant. The TiN nano-material prepared by using the method has the complicated three-dimensional communicated pore passage structure, uniform-thickness tube walls and relatively high specific surface area and pore volume, thus the TiN nano-material with the complicated three-dimensional communicated pore passage structure is expected to have good application prospects in the fields of catalysis and adsorptive separation. The method provided by the invention provides a new way of thinking for the preparation of TiN nano-materials with controllable morphologies and functions.
Description
The present patent application is application number 201210241535.9, the applying date on 07 12nd, 2012, the divisional application of denomination of invention " a kind of titanium nitride nano material and preparation method with three-dimensional communication pore passage structure ".
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to the preparation method of the titanium nitride nano material of a kind of tool high-specific surface area and pore volume.
Background technology
In recent years, about the existing more research of research of nanostructure TiN, but existing report is mainly around preparation and the property research of titanium nitride nano particle and titanium nitride membrane, research about three-dimensional nitride nano-material is little, and the unicity of resulting materials microtexture and pattern has limited its application in industry and field of engineering technology.The biological tissue that biological template nano materials refers to have suitable construction is template, utilizes self-assembly and space confinement effect, forms the both nano material of fixed structure or the process of nanostructure by the method such as physics, chemistry.The structural unit of many biological tissues is all in nanometer range, and these biological structure unit with nanoscale or nano aperture all can be used as template and prepare nano material.Due to the various advantages (size of Nano grade, diversified profile, nature rich content and environmental friendliness etc.) of biomolecules, taking biological tissue as template, the artificial material nano material by self assembly with complicated nanostructure and microscopic appearance is an extremely potential research direction.As the natural fiber element material of the important a member of biological template, the abundantest in distributed in nature, there is unique and complex three-dimensional hierarchical structure, application natural fiber element material is the functional materials that template and skeleton preparation have multilayered structure and pattern, is one and prepares easy, the low cost of functional materials and the synthetic shortcut of environmental protection.
Summary of the invention
The object of the present invention is to provide and a kind ofly there is three-dimensional communication pore passage structure and there is high specific surface area and the preparation method of the titanium nitride nano material of pore volume.
Method provided by the invention is taking natural fiber element material as template, prepares titania nanotube by sol-gel method, then in nitrogen atmosphere, uses MAGNESIUM METAL to reduce as reductive agent gained titanium oxide nanotubes, at high temperature reacts as follows
, generate titanium nitride/magnesium oxide combination product, then remove by product magnesium oxide by dilute acid pretreatment, obtain pure target product titanium nitride nano pipe, specifically comprise the following steps:
(1) under whipped state, successively 36% concentrated hydrochloric acid and tetrabutyl titanate are joined in organic solvent, continue to stir 3 h and make TiO 2 sol.Wherein, raw material is followed tetrabutyl titanate: dense HCl: the mass ratio of organic solvent=7:5:50 ~ 100; Described organic solvent is dehydrated alcohol or dehydrated alcohol/toluene (volume ratio 1:1) mixed solution.
(2) natural fiber prime modulus plate is dipped in above-mentioned solution, leaves standstill after 3 ~ 12 h and take out, deionized water wash number all over after put into 40 ~ 65 ° of C loft drier dried overnight; Dried sample is raised to 450 ~ 600 ° of C roasting 4 ~ 6 h with the temperature rise rate of 2 ° of C/min and removes template and obtain titania nanotube material; Described natural fiber prime modulus plate is the one in quantitative paper, hospital gauze, absorbent cotton.
(3) under room temperature, in nitrogen atmosphere by above gained titania nanotube and MAGNESIUM METAL particle be placed in respectively two ends, left and right in homemade stainless steel cauldron according to the mol ratio of 1:2.5 ~ 4, do not contact each other; Inflated with nitrogen in reactor is rapidly heated to (10 ° of C/min of temperature rise rate) to 1100 ~ 1300 DEG C of maintenance 2 ~ 5 h, rear cool to room temperature except its sealing being put into after net air to tube furnace;
(4) reaction product is processed to 6 ~ 10 h with 1 ~ 2 M dilute acid solution and remove by product MgO, obtain target product; Described diluted acid is dilute hydrochloric acid or rare nitric acid.
Compared with prior art, the present invention has following beneficial effect:
The titanium nitride nano material that the present invention prepares has the nano pore structure of three-dimensional communication, aspect mass transfer, has more advantage than one dimension titanium nitride material.Target product has larger specific surface area and pore volume, and traditional solid nitride powder Particle Phase ratio, has more wide application prospect in catalysis and fractionation by adsorption field.In preparation process, use filter paper, absorbent cotton or gauze for stay in place form, by selecting suitable preparation condition, obtain having in macroscopic view the titanium nitride nano material of scraps of paper shape, cotton-wool dress and gauze shape, these materials with macro morphology can directly be brought application, saved traditional preparation technology product mostly be powder, before use, need the step of further compression moulding.
Brief description of the drawings
Fig. 1 be preparation have three-dimensional communication pore passage structure the SEM figure of titanium nitride nano material.
Fig. 2 be preparation have three-dimensional communication pore passage structure the XRD figure of titanium nitride nano material.
Embodiment
Below by embodiment, the present invention is further described.
Embodiment 1
(1) under whipped state, successively concentrated hydrochloric acid and tetrabutyl titanate are joined in dehydrated alcohol/toluene mixture (volume ratio 1:1), continue to stir 3 h.Wherein, raw material is followed tetrabutyl titanate: the mass ratio of dense HCl: dehydrated alcohol/toluene=7:5:100;
(2) absorbent cotton is dipped in above-mentioned solution, after standing 3 h, takes out, by deionized water wash number time, put into 65 ° of C loft drier dried overnight; Dried sample is raised to 550 ° of C roasting 5 h with the temperature rise rate of 2 ° of C/min and removes template and make titania nanotube material;
(3) under room temperature, in nitrogen atmosphere, gained titania nanotube and MAGNESIUM METAL particle are placed in respectively to two ends, left and right in homemade stainless steel cauldron according to the mol ratio of 1:4, do not contact each other; The 2 h Ex-alls of inflated with nitrogen in reactor are wherein sealed after air, put into tube furnace with the temperature rise rate of 10 ° of C/min be rapidly heated to 1300 DEG C keep 2 h, after be cooled to room temperature;
(4) reaction product is processed to 6 h with 2 M diluted hydrochloric acid aqueous solutions and remove by product MgO, obtain target product.
Embodiment 2
(1) under whipped state, successively concentrated hydrochloric acid and tetrabutyl titanate are joined in dehydrated alcohol/toluene mixture (volume ratio 1:1), continue to stir 3 h.Wherein, raw material is followed tetrabutyl titanate: the mass ratio of dense HCl: dehydrated alcohol/toluene=7:5:100;
(2) medical gauze is dipped in above-mentioned solution, after standing 3 h, takes out, by deionized water wash number time, put into 65 ° of C loft drier dried overnight; Dried sample is raised to 550 ° of C roasting 5 h with the temperature rise rate of 2 ° of C/min and removes template and make titania nanotube material;
(3) under room temperature, in nitrogen atmosphere, gained titania nanotube and MAGNESIUM METAL particle are placed in respectively to two ends, left and right in homemade stainless steel cauldron according to the mol ratio of 1:4, do not contact each other; The 2 h Ex-alls of inflated with nitrogen in reactor are wherein sealed after air, put into tube furnace with the temperature rise rate of 10 ° of C/min be rapidly heated to 1100 DEG C keep 2 h, after be cooled to room temperature;
(4) reaction product is processed to 6 h with 2 M diluted hydrochloric acid aqueous solutions and remove by product MgO, obtain target product.
Claims (1)
1. a preparation method with the nano material of high-specific surface area and pore volume, is characterized in that, according to the following steps:
(1) under whipped state, successively concentrated hydrochloric acid and tetrabutyl titanate are joined in dehydrated alcohol/toluene mixture (volume ratio 1:1), continue to stir 3h; Wherein, tetrabutyl titanate: the mass ratio of dense HCl: dehydrated alcohol/toluene=7:5:100;
(2) absorbent cotton is dipped in above-mentioned solution, after standing 3h, takes out, by deionized water wash number time, put into 65 ° of C loft drier dried overnight; Dried sample is raised to 550 ° of C roasting 5h with the temperature rise rate of 2 ° of C/min left and right and removes template and make titania nanotube material;
(3) under room temperature, in nitrogen atmosphere, gained titania nanotube and MAGNESIUM METAL particle are placed in respectively to two ends, left and right in stainless steel cauldron according to the mol ratio of about 1:4, do not contact each other; Inflated with nitrogen 2h Ex-all in stainless steel cauldron is wherein sealed after air, put into tube furnace with the temperature rise rate of 10 ° of C/min be rapidly heated to 1300 DEG C keep 2 h, after be cooled to room temperature;
(4) reaction product is processed to 6h with 2M diluted hydrochloric acid aqueous solution and remove by product MgO, obtain target product.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210241535.9A CN102701163B (en) | 2012-07-12 | 2012-07-12 | Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material |
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| CN201210241535.9A Division CN102701163B (en) | 2012-07-12 | 2012-07-12 | Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material |
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| CN103864031B CN103864031B (en) | 2015-07-22 |
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| CN201410121032.7A Expired - Fee Related CN103864032B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of nano material |
| CN201410121084.4A Expired - Fee Related CN103864033B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of titanium nitride material |
| CN201210241535.9A Expired - Fee Related CN102701163B (en) | 2012-07-12 | 2012-07-12 | Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material |
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| CN201210241535.9A Expired - Fee Related CN102701163B (en) | 2012-07-12 | 2012-07-12 | Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107675483A (en) * | 2017-09-21 | 2018-02-09 | 东华大学 | A kind of preparation method of the titania nanotube based on click chemistry/bafta catalysis material |
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| CN103450475B (en) * | 2013-09-13 | 2015-10-21 | 中北大学 | The preparation method of core-shell structural conductive polyaniline/Co3O4 powder |
| CN103736475B (en) * | 2014-01-08 | 2015-08-19 | 国家纳米科学中心 | A kind of three-dimensional porous titanium dioxide nano tube catalyst, preparation method and its usage |
| CN105502316B (en) * | 2016-01-30 | 2018-01-12 | 武汉科技大学 | A kind of nitride powder based on low temperature liquid polymerization process and preparation method thereof |
| CN108213461B (en) * | 2017-12-12 | 2021-07-16 | 昆明理工大学 | Preparation method of nano-grade noble metal material |
| CN108298957A (en) * | 2018-02-06 | 2018-07-20 | 叶剑 | A kind of preparation method of 3 D stereo nano material |
| CN110606487A (en) * | 2019-10-16 | 2019-12-24 | 大连理工大学 | Honeycomb three-dimensional porous MXene with controllable pore diameter and general synthesis method thereof |
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| CN101811677B (en) * | 2010-05-06 | 2011-11-09 | 东华大学 | Method for preparing hollow porous quadruped titanium nitride |
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Non-Patent Citations (1)
| Title |
|---|
| 刘效艳等: "天然纤维素为模板的氮化钛纳米管的制备", 《中国化学会第28届学术年会第4分会场摘要集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107675483A (en) * | 2017-09-21 | 2018-02-09 | 东华大学 | A kind of preparation method of the titania nanotube based on click chemistry/bafta catalysis material |
| CN107675483B (en) * | 2017-09-21 | 2019-08-06 | 东华大学 | A kind of preparation method of the titania nanotube based on click chemistry/cotton fabric catalysis material |
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| CN102701163A (en) | 2012-10-03 |
| CN103864031B (en) | 2015-07-22 |
| CN102701163B (en) | 2014-03-19 |
| CN103864033B (en) | 2016-01-20 |
| CN103864032B (en) | 2015-09-23 |
| CN103864033A (en) | 2014-06-18 |
| CN103864032A (en) | 2014-06-18 |
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