CN106587146A - Titanium oxide nanocrystalline aerogel material and preparation method thereof - Google Patents
Titanium oxide nanocrystalline aerogel material and preparation method thereof Download PDFInfo
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- CN106587146A CN106587146A CN201611177040.9A CN201611177040A CN106587146A CN 106587146 A CN106587146 A CN 106587146A CN 201611177040 A CN201611177040 A CN 201611177040A CN 106587146 A CN106587146 A CN 106587146A
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- titanium oxide
- aeroge
- crystalline substance
- tiox nano
- aerogel material
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000004964 aerogel Substances 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 229910003087 TiOx Inorganic materials 0.000 claims description 34
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 33
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000352 supercritical drying Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000004965 Silica aerogel Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention relates to a titanium oxide nanocrystalline aerogel material and a preparation method thereof. The titanium oxide nanocrystalline aerogel material is characterized by having a form of a pale yellow powder, a component of anatase type titanium oxide, a grain size of 7 to 15 nm, a pore size distribution of 10 to 100 nm, a specific surface area of 70 to 130 m<2> / g, and a pore volume of 1.0 to 1.7 cm<3> / g. The preparation method include the steps that tetrabutyl titanate, anhydrous ethanol, deionized water and nitric acid in a certain proportion are subjected to a sol-gel reaction to form a gel, and then the gel is supercritically dried with ethanol to obtain the titanium oxide nanocrystalline aerogel. The preparation process of the invention has the advantages of simple process, low cost and easy scale production. The prepared titanium oxide nanocrystalline aerogel material has a higher specific surface area and good structural stability.
Description
Technical field
The invention belongs to the preparation technology field of aeroge nano-porous materials, is related to a kind of TiOx nano crystalline substance aeroge
Material and preparation method thereof.
Background technology
Aeroge is the nano-porous materials that a kind of nano-particle is mutually assembled, with high-specific surface area, low-density,
Many excellent properties such as high porosity, have good application prospect in fields such as heat-insulated, absorption, catalysis.Titanium oxide is a kind of property
The excellent catalyst of energy, is widely studied in photocatalysis field.But current business-like titanium oxide catalyst (P25) specific surface
Product is relatively low.Although titania aerogel is with higher specific surface area, its aerogel products mostly is amorphous materialses, in order to
To make it have photocatalysis effect and must carry out follow-up heat treatment make its crystallization, and crystallization process can heavy damage aeroge
Pore structure so as to which specific surface area is greatly lowered.
The content of the invention
The invention aims to make up the shortcoming on existing titanium oxide catalyst material structure, improve existing titanium oxide
The deficiency that aeroge technology of preparing is present, there is provided a kind of high-specific surface area, the TiOx nano crystalline substance aeroge of good thermal stability
Material, it is a further object of the present invention to provide the preparation method of above-mentioned TiOx nano crystalline substance aerogel material, the letter of the method technique
Single, synthesis cycle is short, low cost, can directly prepare crystalline titanium oxide aerogel material.
The object of the invention technical scheme is：A kind of TiOx nano crystalline substance aerogel material, it is characterised in that its form is light
Yellow powder, composition are anatase-type titanium oxide, and 7～15nm of crystallite dimension, pore-size distribution exist in 10～100nm, specific surface area
70～130m2/ g, 1.0～1.7cm of pore volume3/g。
Present invention also offers the method for above-mentioned TiOx nano crystalline substance aeroge, which comprises the following steps that：
(1) solution is obtained after being uniformly mixed nitric acid, dehydrated alcohol and deionized water under room temperature；
(2), in the solution for adding step (1) to obtain butyl titanate, continue stirring and obtain solution；
(3) solution obtained in step (2) obtains titanium oxide gel in 6～24 hours in 50～60 DEG C of reactions；
(4) titanium oxide gel obtains TiOx nano crystalline substance aeroge using supercritical drying.
It is preferred that the mol ratio of above-mentioned raw materials butyl titanate, dehydrated alcohol, deionized water and nitric acid is 1：(20～30)：(2
～6)：(0.2～0.4).
Speed of agitator in preferred steps (1) is 500～2000rpm, and mixing time is 1～5 minute；In step (2)
Speed of agitator is 500～2000rpm, and mixing time is 10～60 minutes.
Supercritical drying parameter described in preferred steps (4) is：8～12MPa of pressure, 250～270 DEG C of temperature.
Beneficial effect：
(1) relative to the P25 titanium oxide crystal catalysts of commercialization, TiOx nano crystalline substance aeroge has higher ratio table
Area and more preferable structural stability；Relative to titanium oxide gas prepared by traditional amorphous titanium aerogel material, the present invention
Gel is nanocrystalline, and being not required to follow-up heat treatment makes its crystallization.
(2) relative to conventional oxidation Silica Aerogels TiOx nano crystalline substance aeroge preparation process is simple, directly can make
Standby oxidation titanium crystal.
(3) equipment is simple, and raw material is easy to get, with low cost, easily accomplishes scale production.
Description of the drawings
Fig. 1 is the XRD characterization results of TiOx nano crystalline substance aeroge obtained in example 1.
Fig. 2 is the Pore Characterization that TiOx nano crystalline substance aeroge and business-like P25 obtained in example 1 aoxidize titanium crystal
Comparison diagram.
Fig. 3 is the pore-size distribution of TiOx nano crystalline substance aeroge sample after different temperatures heat treatment obtained in example 1.
Fig. 4 is the SEM photograph of TiOx nano crystalline substance aeroge obtained in example 2.
Specific embodiment
Example 1
After 5 minutes mix homogeneously, then nitric acid, dehydrated alcohol and deionized water is stirred with the rotating speed of 500rpm under room temperature
Add butyl titanate to continue and mixed solution, wherein the mol ratio metatitanic acid of raw material are obtained for 30 minutes with the rotating speed stirring of 1500rpm
Four butyl esters:Dehydrated alcohol:Deionized water:Nitric acid=1:25:4:0.3；Mixed solution reacts 12 hours at 55 DEG C and is aoxidized
Titanium gel；Titanium oxide gel obtains crystallite dimension 8nm, specific surface area and is through 10MPa, 260 DEG C of ethanol supercritical dryings
110m2/ g, pore-size distribution is in 30～100nm, pore volume 1.5cm3The TiOx nano crystalline substance aeroge of/g.
Referring to accompanying drawing, the XRD test results of TiOx nano crystalline substance aeroge obtained in present example 1 in Fig. 1, are given.
As can be seen that titania aerogel is anatase structured.
Referring to accompanying drawing, TiOx nano crystalline substance aeroge and business-like P25 obtained in present example 1 in Fig. 2, are given
The Pore Characterization comparison diagram of oxidation titanium crystal.The TiOx nano that present invention preparation be can be seen that from pore structure comparison diagram is brilliant
Aeroge has more preferable pore structure.
Referring to accompanying drawing, Fig. 3 is TiOx nano crystalline substance aeroge obtained in example 1 through different temperatures heat treatment (3 in air
Hour) pore-size distribution of sample afterwards.As can be seen that TiOx nano crystalline substance aeroge has good structural stability, high warm
Process to its pore structure without damaging influence.
Example 2
Nitric acid, dehydrated alcohol and deionized water are stirred after 3 minutes mix homogeneously, so with the rotating speed of 1000rpm under room temperature
Add butyl titanate to continue afterwards and mixed solution, wherein the mol ratio titanium of raw material are obtained for 10 minutes with the rotating speed stirring of 2000rpm
Sour four butyl esters:Dehydrated alcohol:Deionized water:Nitric acid=1:20:6:0.4；Mixed solution reacts 24 hours at 50 DEG C and obtains oxygen
Change titanium gel；Titanium oxide gel obtains crystallite dimension 9nm, specific surface area and is through 8MPa, 270 DEG C of ethanol supercritical dryings
130m2/ g, pore-size distribution is in 10～80nm, pore volume 1.7cm3The TiOx nano crystalline substance aeroge of/g.
Referring to accompanying drawing, SEM photographs of the Fig. 4 for TiOx nano crystalline substance aeroge obtained in example 2.Can be with from SEM photograph
Find out, the TiOx nano crystalline substance aeroge prepared by the present invention has the typical meso-hole structure feature of aerogel material, its granule
Uniform in size, pore structure is good.
Example 3
Nitric acid, dehydrated alcohol and deionized water are stirred after 1 minute mix homogeneously, so with the rotating speed of 1500rpm under room temperature
Add butyl titanate to continue afterwards and mixed solution, wherein the mol ratio metatitanic acid of raw material are obtained for 60 minutes with the rotating speed stirring of 500rpm
Four butyl esters:Dehydrated alcohol:Deionized water:Nitric acid=1:30:2:0.2；Mixed solution reacts 6 hours at 60 DEG C and obtains titanium oxide
Gel；Titanium oxide gel obtains crystallite dimension 12nm, specific surface area for 70m through 12MPa, 250 DEG C of ethanol supercritical dryings2/
G, pore-size distribution is in 10～70nm, pore volume 1.0cm3The TiOx nano crystalline substance aeroge of/g.Jing XRD are tested, it can be seen that oxygen
It is anatase structured to change titanium aeroge.From on SEM photograph as can be seen that prepared TiOx nano crystalline substance aeroge has airsetting
The typical meso-hole structure feature of glue material, its even particle size, pore structure are good.TiOx nano crystalline substance aeroge has good
Structural stability, high-temperature heat treatment is to its pore structure without damaging influence.
Example 4
Nitric acid, dehydrated alcohol and deionized water are stirred after 1 minute mix homogeneously, so with the rotating speed of 1500rpm under room temperature
Add butyl titanate to continue afterwards and mixed solution, wherein the mol ratio titanium of raw material are obtained for 40 minutes with the rotating speed stirring of 1000rpm
Sour four butyl esters:Dehydrated alcohol:Deionized water:Nitric acid=1:30:4:0.3；Mixed solution reacts 18 hours at 55 DEG C and obtains oxygen
Change titanium gel；Titanium oxide gel obtains crystallite dimension 10nm, specific surface area and is through 10MPa, 260 DEG C of ethanol supercritical dryings
100m2/ g, pore-size distribution is in 20～90nm, pore volume 1.4cm3The TiOx nano crystalline substance aeroge of/g.Jing XRD are tested, and can be seen
It is anatase structured to go out titania aerogel.From on SEM photograph as can be seen that prepared TiOx nano crystalline substance aeroge has
The typical meso-hole structure feature of aerogel material, its even particle size, pore structure are good.TiOx nano crystalline substance aeroge has
Good structural stability, high-temperature heat treatment is to its pore structure without damaging influence.
Example 5
Nitric acid, dehydrated alcohol and deionized water are stirred after 1 minute mix homogeneously, so with the rotating speed of 2000rpm under room temperature
Add butyl titanate to continue afterwards and mixed solution, wherein the mol ratio titanium of raw material are obtained for 20 minutes with the rotating speed stirring of 2000rpm
Sour four butyl esters:Dehydrated alcohol:Deionized water:Nitric acid=1:28:4:0.3；Mixed solution reacts 24 hours at 60 DEG C and obtains oxygen
Change titanium gel；Titanium oxide gel obtains crystallite dimension 11nm, specific surface area and is through 12MPa, 270 DEG C of ethanol supercritical dryings
92m2/ g, pore-size distribution is in 10～90nm, pore volume 1.2cm3The TiOx nano crystalline substance aeroge of/g.Jing XRD are tested, and can be seen
It is anatase structured to go out titania aerogel.From on SEM photograph as can be seen that prepared TiOx nano crystalline substance aeroge has
The typical meso-hole structure feature of aerogel material, its even particle size, pore structure are good.TiOx nano crystalline substance aeroge has
Good structural stability, high-temperature heat treatment is to its pore structure without damaging influence.
Claims (5)
1. a kind of TiOx nano crystalline substance aerogel material, it is characterised in that its form is pale yellow powder, and composition is Detitanium-ore-type
Titanium oxide, 7～15nm of crystallite dimension, in 10～100nm, specific surface area is in 70～130m for pore-size distribution2/ g, pore volume 1.0～
1.7cm3/g。
2. a kind of method for preparing TiOx nano as claimed in claim 1 crystalline substance aeroge, which comprises the following steps that：
(1) solution is obtained after being uniformly mixed nitric acid, dehydrated alcohol and deionized water；
(2), in the solution for adding step (1) to obtain butyl titanate, continue stirring and obtain solution；
(3) solution obtained in step (2) obtains titanium oxide gel in 6～24 hours in 50～60 DEG C of reactions；
(4) titanium oxide gel obtains TiOx nano crystalline substance aeroge using supercritical drying.
3. method according to claim 2, it is characterised in that raw materials used mol ratio is butyl titanate：Anhydrous second
Alcohol：Deionized water：Nitric acid=1：(20～30)：(2～6)：(0.2～0.4).
4. method according to claim 2, it is characterised in that the speed of agitator in step (1) is 500～2000rpm, is stirred
The time is mixed for 1～5 minute；Speed of agitator in step (2) is 500～2000rpm, and mixing time is 10～60 minutes.
5. method according to claim 2, it is characterised in that the supercritical drying parameter described in step (4) is：Pressure 8
～12MPa, 250～270 DEG C of temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611177040.9A CN106587146A (en) | 2016-12-19 | 2016-12-19 | Titanium oxide nanocrystalline aerogel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611177040.9A CN106587146A (en) | 2016-12-19 | 2016-12-19 | Titanium oxide nanocrystalline aerogel material and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN106587146A true CN106587146A (en) | 2017-04-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892420A (en) * | 2020-07-29 | 2020-11-06 | 南京工业大学 | Method for preparing massive titanium carbide, titanium nitride or titanium carbonitride aerogel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810356A (en) * | 2006-03-02 | 2006-08-02 | 复旦大学 | Prepn process of nanometer crystal titania aerogel with high photocatalysis activity |
| US8497199B1 (en) * | 2012-06-01 | 2013-07-30 | Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan | Method for fabricating a thin film formed with a uniform single-size monolayer of spherical AZO nanoparticles |
-
2016
- 2016-12-19 CN CN201611177040.9A patent/CN106587146A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810356A (en) * | 2006-03-02 | 2006-08-02 | 复旦大学 | Prepn process of nanometer crystal titania aerogel with high photocatalysis activity |
| US8497199B1 (en) * | 2012-06-01 | 2013-07-30 | Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan | Method for fabricating a thin film formed with a uniform single-size monolayer of spherical AZO nanoparticles |
Non-Patent Citations (2)
| Title |
|---|
| YONG KONG等: "Direct synthesis of anatase TiO2 aerogel resistant to high temperature under supercritical ethanol", 《MATERIALS LETTERS》 * |
| 林本兰等: "锐钛矿型TiO2 气凝胶的制备和光催化性能", 《南京工业大学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892420A (en) * | 2020-07-29 | 2020-11-06 | 南京工业大学 | Method for preparing massive titanium carbide, titanium nitride or titanium carbonitride aerogel |
| CN111892420B (en) * | 2020-07-29 | 2022-05-03 | 南京工业大学 | Method for preparing massive titanium carbide, titanium nitride or titanium carbonitride aerogel |
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Application publication date: 20170426 |