CN102701163B - Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material - Google Patents
Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material Download PDFInfo
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- CN102701163B CN102701163B CN201210241535.9A CN201210241535A CN102701163B CN 102701163 B CN102701163 B CN 102701163B CN 201210241535 A CN201210241535 A CN 201210241535A CN 102701163 B CN102701163 B CN 102701163B
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Abstract
The invention relates to a titanium nitride nanometer material having a three-dimensional connected pore channel structure and a preparation method of the titanium nitride nanometer material and belongs to the technical field of inorganic nanometer materials. The preparation method comprises the following steps: preparing a titanium dioxide nanometer tube having the similar micro-morphology and hierarchical structure with a cellulose material by taking the natural cellulose material as a template and taking tetrabutyl titanate as a titanium precursor, and then preparing a TiN nanometer material having the three-dimensional connected pore channel structure by a magnesium thermal reduction method in a high temperature (110 DEG C-1300 DEG C) tube type furnace by utilizing magnesium metal as a reducing agent. The TiN nanometer material prepared by the preparation method has the complex three-dimensional connected pore channel structure, the tube wall with uniform thickness and high specific surface area and pore volume, thus the TiN nanometer material having the three-dimensional connected pore channel structure is expected to have good application prospect in the fields of catalysis and adsorption separation. The preparation method provided by the invention provides a new idea for preparing the TiN nanometer material with controllable morphology and function.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to a kind of titanium nitride nano material and preparation method with three-dimensional communication pore passage structure.
Background technology
Titanium nitride (TiN) is a kind of transition metal nitride, there is B1-NaCl type crystal structure, because of its excellent physics and chemistry character, high rigidity for example, high-melting-point, good specific conductivity, thermal conductivity and erosion resistance, and high chemical stability, in engineering application aspect, there is important using value, therefore receive investigator's very big concern.In recent years, the existing more research of research about nanostructure TiN, but existing report is mainly around preparation and the property research of titanium nitride nano particle and titanium nitride membrane, about the research of three-dimensional nitride nano-material but seldom, the unicity of resulting materials microtexture and pattern has limited its application in industry and field of engineering technology.Therefore, research and develop the novel TiN nano material with three-dimensional structure and complex topography imperative to meet the active demand of actual production and life.
The biological tissue that biological template nano materials refers to have suitable construction is template, utilizes self-assembly and space confinement effect, by methods such as physics, chemistry, forms the both nano material of fixed structure or the process of nanostructure.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.Various advantages (size of Nano grade, diversified profile, nature rich content and environmental friendliness etc.) due to biomolecules, take biological tissue as template, and the artificial material nano material by self assembly with complicated nanostructure and microscopic appearance is an extremely potential research direction.Natural fiber element material as 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.
Magnesium reduction process is the process that a little less than utilizing magnesium metal reduction activity, the compound of metal is produced metal simple-substance or its alloy, and reaction process is simple, and intermediate product magnesium oxide only need can be removed by simple acid treatment.Chinese invention patent CN101357762A, CN101348242A and CN102259858 describe respectively the method for using magnesium reduction process to prepare zirconium carbide powder, boron nitride nano-tube and porous elemental silicon in detail.At present, magnesium reduction process has very consequence in field of material preparation.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of and 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 that to take natural fiber element material be template, by sol-gel method, prepares titania nanotube, then in nitrogen atmosphere, uses MAGNESIUM METAL to reduce as reductive agent gained titanium oxide nanotubes, at high temperature reacts as follows 2TiO
2+ 4Mg+N
2→ 2TiN+4MgO, generates titanium nitride/magnesium oxide combination product, then by dilute acid pretreatment, removes by product magnesium oxide, obtains pure target product titanium nitride nano pipe, specifically comprises the following steps:
(1) under whipped state, successively 36% concentrated hydrochloric acid and tetrabutyl titanate are joined in organic solvent, continue to stir 3h and make TiO 2 sol.Wherein, raw material is followed tetrabutyl titanate: dense HCl: the mass ratio of organic solvent=7:5:50 ~ 100;
(2) natural fiber prime modulus plate is dipped in above-mentioned solution, after standing 3 ~ 12h, takes 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 ~ 6h with the temperature rise rate of 2 ° of C/min and removes template and obtain titania nanotube material;
(3) under room temperature, in nitrogen atmosphere by above gained titania nanotube and MAGNESIUM METAL particle according to the mol ratio of 1:2.5 ~ 4, be placed in respectively two ends, left and right in homemade stainless steel cauldron, 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 ℃ of maintenance 2 ~ 5h, rear cool to room temperature except its sealing being put into after net air to tube furnace;
(4) reaction product is processed to 6 ~ 10h with 1 ~ 2M dilute acid solution and remove by product MgO, obtain target product.
In the present invention, organic solvent described in step (1) is dehydrated alcohol or dehydrated alcohol/toluene (volume ratio 1:1) mixed solution.
In the present invention, natural fiber prime modulus plate described in step (2) is a kind of in quantitative paper, hospital gauze, absorbent cotton.
In the present invention, diluted acid described in step (4) is dilute hydrochloric acid or rare nitric acid.
Compared with prior art, the present invention has following beneficial effect:
1, the titanium nitride nano material that the present invention prepares has the nano pore structure of three-dimensional communication, aspect mass transfer, than one dimension titanium nitride material, has more advantage.
2, target product has larger specific surface area and pore volume, and traditional solid nitride powder Particle Phase ratio, in catalysis and fractionation by adsorption field, has more wide application prospect.
3, 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.
Accompanying drawing explanation
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 36% concentrated hydrochloric acid and tetrabutyl titanate are joined in dehydrated alcohol, continue to stir 3h and make TiO 2 sol.Wherein, tetrabutyl titanate: the mass ratio of dense HCl: dehydrated alcohol=7:5:100;
(2) the common quantitative paper of use for laboratory 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 and removes template and obtain titania nanotube material;
(3) under room temperature, in nitrogen atmosphere, gained titania nanotube and MAGNESIUM METAL particle are above placed in respectively to two ends, left and right in homemade stainless steel cauldron according to the mol ratio of 1:2.5, do not contact each other; Inflated with nitrogen 2h Ex-all in reactor is wherein sealed after air, puts into tube furnace and be rapidly heated to 1200 ℃ and keep 2h with the temperature rise rate of 10 ° of C/min, 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.
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 3h.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 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 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; Inflated with nitrogen 2h Ex-all in reactor is wherein sealed after air, puts into tube furnace and be rapidly heated to 1300 ℃ and keep 2h with the temperature rise rate of 10 ° of C/min, 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.
Embodiment 3
(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, 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 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 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; Inflated with nitrogen 2h Ex-all in reactor is wherein sealed after air, puts into tube furnace and be rapidly heated to 1100 ℃ and keep 2h with the temperature rise rate of 10 ° of C/min, 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.
Embodiment 4
(1) under whipped state, successively concentrated hydrochloric acid and tetrabutyl titanate are joined in dehydrated alcohol, continue to stir 3h.Wherein, tetrabutyl titanate: the mass ratio of dense HCl: dehydrated alcohol=7:5:50;
(2) the common quantitative paper of use for laboratory 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 and removes template and obtain titania nanotube material;
(3) under room temperature, in nitrogen atmosphere, gained titania nanotube and MAGNESIUM METAL particle are above placed in respectively to two ends, left and right in homemade stainless steel cauldron according to the mol ratio of 1:2.5, do not contact each other; Inflated with nitrogen 2h Ex-all in reactor is wherein sealed after air, puts into tube furnace and be rapidly heated to 1300 ℃ and keep 2h with the temperature rise rate of 10 ° of C/min, after be cooled to room temperature;
(4) reaction product is processed to 10h with 1M diluted nitric acid aqueous solution and remove by product MgO, obtain target product.
Claims (1)
1. a preparation method with the titanium nitride nano material of three-dimensional communication pore passage structure, is characterized in that, as follows:
(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, tetrabutyl titanate: dense HCl: the mass ratio of organic solvent=7:5:50 ~ 100; Described organic solvent is dehydrated alcohol/toluene mixture liquid of dehydrated alcohol or volume ratio 1:1;
(2) natural fiber prime modulus plate is dipped in above-mentioned solution, after standing 3 ~ 12 h, takes 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 a kind of in quantitative paper, hospital gauze, absorbent cotton;
(3) under room temperature, in nitrogen atmosphere by above gained titania nanotube and MAGNESIUM METAL particle according to the mol ratio of 1:2.5 ~ 4, be placed in respectively two ends, left and right in stainless steel cauldron, do not contact each other; Inflated with nitrogen in stainless steel cauldron is rapidly heated to 1100 ~ 1300 ℃ of maintenance 2 ~ 5 h, rear cool to room temperature except its sealing being put into after net air to tube furnace; Described temperature rise rate in tube furnace is 10 ° of C/min;
(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.
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| CN201410120722.0A CN103864031B (en) | 2012-07-12 | 2012-07-12 | Method for preparing nano-material with high specific surface area and pore volume |
| CN201410121032.7A CN103864032B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of nano material |
| 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 |
| CN201410121084.4A CN103864033B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of titanium nitride material |
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| CN201410121084.4A Division CN103864033B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of titanium nitride material |
| CN201410121032.7A Division CN103864032B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of nano material |
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| CN201410120722.0A Expired - Fee Related CN103864031B (en) | 2012-07-12 | 2012-07-12 | Method for preparing nano-material with high specific surface area and pore volume |
| CN201410121032.7A Expired - Fee Related CN103864032B (en) | 2012-07-12 | 2012-07-12 | A kind of preparation method of nano 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 |
| 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 |
| 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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