CN105664987A - Synthetic method of nano ceramic and nano carbide composite material - Google Patents
Synthetic method of nano ceramic and nano carbide composite material Download PDFInfo
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- CN105664987A CN105664987A CN201410675780.XA CN201410675780A CN105664987A CN 105664987 A CN105664987 A CN 105664987A CN 201410675780 A CN201410675780 A CN 201410675780A CN 105664987 A CN105664987 A CN 105664987A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000011651 chromium Substances 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910003470 tongbaite Inorganic materials 0.000 claims description 9
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910039444 MoC Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- NFYLSJDPENHSBT-UHFFFAOYSA-N chromium(3+);lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[La+3] NFYLSJDPENHSBT-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229910052721 tungsten Inorganic materials 0.000 abstract 2
- 239000010937 tungsten Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910017563 LaCrO Inorganic materials 0.000 description 2
- 229910002262 LaCrO3 Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229910002287 La2Mo2O9 Inorganic materials 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a synthetic method of a nano ceramic and nano carbide composite material. The synthetic method includes the following steps: (1) weighing a metal salt, and fully stirring and dissolving the metal salt to obtain a solution A; (2) weighing a complex agent, and adding water to dissolve the complex agent with stirring to obtain a solution B; (3) slowly adding the solution B to the solution A, continuously stirring the mixture solution, and heat-evaporating the solution to form a sol; (4) pouring the sol into an evaporation dish, heating and combusting the sol to obtain a composite oxide initial powder containing tungsten, chromium and molybdenum, and calcining the composite oxide initial powder at 500-1000 DEG C to obtain a composite material of the nano ceramic and the oxide containing the tungsten, chromium and molybdenum; and (5) performing temperature-programmed reduction under a reducing atmosphere, maintaining the status for 1-50 h, and rapidly reducing the temperature to room temperature under the reducing atmosphere to obtain the nano ceramic and nano carbide composite material. With addition of the nano ceramic, the carbide can be effectively stabilized. With change of metal ratio, the size of the carbide can be effectively controlled within a few nanometers to hundreds of nanometers.
Description
Technical field
The invention belongs to field of nanometer technology, be specifically related to a kind of nano ceramics and the synthetic method of nano-carbide composite.
Technical background
Carbide is a kind of to be had between metal-like properties and fills compound, and namely the carbon atom of small volume occupies the space of metallic atom closs packing layer, formation there is simple crystal structure. Carbide, because of its electronic structure with uniqueness and surface nature, can show the catalytic performance of class noble metal in catalytic reaction. It is mainly used in synthesis and decomposition reaction energy (such as tungsten carbide, molybdenum carbide etc.) of hydrogenation/dehydrogenation reaction, hydrodesulfurization/hydrodenitrogeneration reaction, ammonia, is that people study the important research direction substituting precious metal material; In addition, carbide or a class have the material of significantly high fusing point and hardness, high heat stability and mechanical stability, the at room temperature almost feature such as resistance to various chemical attacks, are therefore widely used in machine cut, mineral mining, manufacture wear-resistant and the field such as high-temperature component and nuclear reactor (such as chromium carbide, zirconium carbide etc.). At present, the method preparing carbide specifically includes that direct carborization, self-propagating high-temperature synthesis, high-energy ball milling method, temperature programming carbonizatin method etc. Wherein, the advantages such as temperature programming carbonizatin method is simple to operate, controllability is strong and be widely used. But the carbide size that all of preparation method obtains all is difficult to control to, and size is generally at micron order, is easy to loss of activity in catalytic reaction. It addition, current research person lacks the research on the impact of its catalytic performance of carbide size controllable pair.
Summary of the invention
For the problems referred to above, the present invention provides a kind of nano ceramics and the synthetic method of nano-carbide composite. The method by the interpolation of nano ceramics can effective stable carbide, and along with carbide size can be control effectively to hundreds of nanometers by change metal proportioning at several nanometers. And catalysis activity is had material impact by the interfacial effect of nano-carbide and nano ceramics.
The present invention adopts the following technical scheme that realization: the synthetic method of a kind of nano ceramics and nano-carbide composite, comprises the steps:
(1) weighing the slaine of nano ceramics and the presoma of nano-carbide, adding water is sufficiently stirred for dissolving and obtains solution A;
(2) weigh chelating agent to add water stirring and dissolving, obtain solution B;
(3) solution B is slowly added in solution A, continues stirring and solution heating evaporation is formed colloidal sol;
(4) pouring in evaporating dish by colloidal sol, heating by electric cooker burning obtains tungstenic, chromium, molybdenum composite oxides just powder, then it is obtained nano ceramics and tungstenic, chromium, molybdenum oxide composite in 2 hours at 500～1000 DEG C of temperature lower calcinations;
(5) carry out temperature programmed reduction process under reducing atmosphere, and keep 1～50h, be then rapidly decreased to room temperature under a reducing atmosphere, obtain nano ceramics and nano-carbide composite.
The slaine of described nano ceramics is one or two or more kinds in Yttrium trinitrate, Lanthanum (III) nitrate, strontium nitrate, zirconium nitrate, cerous nitrate, Gadolinium trinitrate, cobalt nitrate or ferric nitrate, and the precursor of described nano-carbide is one or two or more kinds in ammonium tungstate, ammonium molybdate, chromic nitrate; It is 10:1～1:10 that the proportioning of the slaine of described nano ceramics and the precursor of nano-carbide meets the composite oxides mass ratio of nano ceramics and tungstenic, chromium or molybdenum.
Described chelating agent is the one of ethylenediaminetetraacetic acid, triethanolamine, tartaric acid, citric acid, ammonium citrate, oxalic acid, polyacrylic acid etc. or two or more, and the mol ratio of chelating agent and metal ion total amount is 1:1～10:1.
It is a kind of or two or more that described nano ceramics is mainly the zirconium oxide (YSZ) of stabilized with yttrium oxide, the cerium oxide (GDC) of Gadolinia. doping, the cerium oxide (LDC) of lanthanum oxide doping, lanthanum-strontium ferro-cobalt (LSCF) etc.; Tungstenic, chromium, molybdenum oxide are mainly one or more of tungsten oxide, chromium oxide, molybdenum oxide, lanthanum molybdate, Lanthanum Chromite etc.; Nano-carbide is mainly the one of tungsten carbide, chromium carbide, molybdenum carbide etc. or two or more.
Described reducing atmosphere is volume fraction to be methane, ethane, propane, the hydro carbons such as normal butane a kind of of 1～50% or plants the gaseous mixture of above gas and hydrogen.
The temperature of Temperature Programmed Processes of the present invention is 400～1000 DEG C, and heating rate is 0.5～10 DEG C/min.
Described nano ceramics is with the composite of nano-carbide, and nano-carbide is of a size of 5nm～200nm.
The present invention has such advantages as relative to prior art and effect:
(1) a kind of method synthesized altogether by collosol and gel obtains tungstenic, chromium, molybdenum composite oxides just powder, then it is obtained at 500～1000 DEG C of temperature lower calcinations nano ceramics and tungstenic, chromium, molybdenum oxide material, carry out selectivity carbonization by temperature-programmed reduction method, obtain nano ceramics and nano-carbide composite.
(2) the method by the interpolation of nano ceramics can effective stable carbide, and along with carbide size can be control effectively to hundreds of nanometers by change metal proportioning at several nanometers.
(3) while regulating carbide size, increasing both contacts area, interfacial effect strengthens catalytic performance.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) it is that 40:60 ratio accurately weighs 10.5gLa (NO in nano ceramics and chromium-containing oxide mass ratio3)3·6H2O、10gCr(NO3)3·9H2O、2gY(NO3)3·6H2O、12gZr(NO3)4·5H2O, adds deionized water and is sufficiently stirred for until dissolving, obtain solution A;
(2) weigh 16.5g ethylenediaminetetraacetic acid, add deionized water and be sufficiently stirred for until dissolving, obtain solution B;
(3) above-mentioned solution B is slowly added in solution A, and is 2 with concentrated nitric acid adjustment pH value, heat slow evaporation solution;
(4) to be heated be evaporated to formation colloidal sol after pour in evaporating dish, form composite oxide of metal just powder with heating by electric cooker burning;
(5) zirconium oxide (YSZ) and the chromium-containing oxide Lanthanum Chromite (LaCrO of nano ceramics stabilized with yttrium oxide are obtained at 500 DEG C after being calcined 2 hours by first powder3), and YSZ:LaCrO3Mass ratio 40:60;
(6) the sample tabletting after calcining being pulverized and sieved, taking 60～80 order sample 200mg in the crystal reaction tube of internal diameter 3mm, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then at 20%CH4/H2It is warming up to 600 DEG C with 1 DEG C/min of heating rate from 400 DEG C under (volume fraction) atmosphere and keeps 4 hours, then under this reducing atmosphere, it is rapidly cooled to room temperature, obtain the composite of YSZ-chromium carbide, its YSZ size of high power scanning electron microscopic observation is about 40nm, and chromium carbide size is about 20nm.
Embodiment 2
(1) it is that 70:30 ratio accurately weighs 4.2gLa (NO in nano ceramics and molybdenum-containing oxide mass ratio3)3·6H2O、1.72g(NH4)6Mo7O24·4H2O、3.26gY(NO3)3·6H2O、21.1gZr(NO3)4·5H2O, adds deionized water and is sufficiently stirred for until dissolving, obtain solution A;
(2) weigh 31.5g polyacrylic acid, add deionized water and be sufficiently stirred for until dissolving, obtain solution B;
(3) above-mentioned solution B is slowly added in solution A, and is 2 with concentrated nitric acid adjustment pH value, heat slow evaporation solution;
(4) to be heated be evaporated to formation colloidal sol after pour in evaporating dish, form composite oxide of metal just powder with heating by electric cooker burning;
(5) zirconium oxide (YSZ) and the molybdenum-containing oxide lanthanum molybdate (La of nano ceramics stabilized with yttrium oxide are obtained at 800 DEG C after being calcined 2 hours by first powder2Mo2O9), and YSZ:La2Mo2O9Mass ratio 70:30;
(6) the sample tabletting after calcining being pulverized and sieved, taking 60～80 order sample 200mg in the crystal reaction tube of internal diameter 3mm, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then at 20%CH4/H2It is warming up to 800 DEG C with 2 DEG C/min of heating rates from 400 DEG C under (volume fraction) atmosphere and keeps 2 hours, then under this reducing atmosphere, it is rapidly cooled to room temperature, obtain the composite of YSZ-molybdenum carbide, its YSZ size of high power scanning electron microscopic observation is about 20nm, and molybdenum carbide size is about 10nm.
Embodiment 3
(1) 4.24g (NH is accurately weighed with tungstenic oxide mass than for 50:50 ratio in nano ceramics4)10W12O41·4H2O、2.35gY(NO3)3·6H2O、14.9gZr(NO3)4·5H2O, adds deionized water and is sufficiently stirred for until dissolving, obtain solution A;
(2) weigh 37.5g ammonium citrate, add deionized water and be sufficiently stirred for until dissolving, obtain solution B;
(3) above-mentioned solution B is slowly added in solution A, and is 3 with concentrated nitric acid adjustment pH value, heat slow evaporation solution;
(4) to be heated be evaporated to formation colloidal sol after pour in evaporating dish, form composite oxide of metal just powder with heating by electric cooker burning;
(5) zirconium oxide (YSZ) and the tungsten oxide (WO of nano ceramics stabilized with yttrium oxide are obtained at 700 DEG C after being calcined 2 hours by first powder3), and YSZ:WO3Mass ratio 50:50;
(6) the sample tabletting after calcining being pulverized and sieved, taking 60～80 order sample 200mg in the crystal reaction tube of internal diameter 3mm, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then at 5%C4H10/H2It is warming up to 700 DEG C with 5 DEG C/min of heating rates from 400 DEG C under (volume fraction) atmosphere and keeps 8 hours, then under this reducing atmosphere, it is rapidly cooled to room temperature, obtain the composite of YSZ-tungsten carbide, its YSZ size of high power scanning electron microscopic observation is about 30nm, and tungsten carbide size is about 15nm.
Embodiment 4
(1) it is that 80:20 ratio accurately weighs 10gCr (NO in nano ceramics and chromium-containing oxide mass ratio3)3·9H2O、3.73gY(NO3)3·6H2O、24.2gZr(NO3)4·5H2O, adds deionized water and is sufficiently stirred for until dissolving, obtain solution A;
(2) weigh 20.1g citric acid, add deionized water and be sufficiently stirred for until dissolving, obtain solution B;
(3) above-mentioned solution B is slowly added in solution A, and is 4 with concentrated nitric acid adjustment pH value, heat slow evaporation solution;
(4) to be heated be evaporated to formation colloidal sol after pour in evaporating dish, form composite oxide of metal just powder with heating by electric cooker burning;
(5) zirconium oxide (YSZ) and the chromium oxide (Cr of nano ceramics stabilized with yttrium oxide are obtained at 900 DEG C after being calcined 2 hours by first powder2O3), and YSZ:Cr2O3Mass ratio 80:20;
(6) the sample tabletting after calcining being pulverized and sieved, taking 60～80 order sample 200mg in the crystal reaction tube of internal diameter 3mm, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then at 20%CH4/H2It is warming up to 900 DEG C with 2 DEG C/min of heating rates from 400 DEG C under (volume fraction) atmosphere and keeps 2 hours, then under this reducing atmosphere, it is rapidly cooled to room temperature, obtain the composite of YSZ-chromium carbide, its YSZ size of high power scanning electron microscopic observation is about 50nm, and chromium carbide size is about 7nm.
Embodiment 5
(1) it is that 40:60 ratio accurately weighs 10.5gLa (NO in nano ceramics and chromium-containing oxide mass ratio3)3·6H2O、10gCr(NO3)3·9H2O、7.8Ce(NO3)3·6H2O、2.1gGd(NO3)3·6H2O, adds deionized water and is sufficiently stirred for until dissolving, obtain solution A;
(2) weigh 20.4g ethylenediaminetetraacetic acid, add deionized water and be sufficiently stirred for until dissolving, obtain solution B;
(3) above-mentioned solution B is slowly added in solution A, and is 2 with concentrated nitric acid adjustment pH value, heat slow evaporation solution;
(4) to be heated be evaporated to formation colloidal sol after pour in evaporating dish, form composite oxide of metal just powder with heating by electric cooker burning;
(5) cerium oxide (GDC) and the chromium-containing oxide Lanthanum Chromite (LaCrO of the doping of nano ceramics Gadolinia. are obtained at 500 DEG C after being calcined 2 hours by first powder3), and GDC:LaCrO3Mass ratio 40:60;
(6) the sample tabletting after calcining being pulverized and sieved, taking 60～80 order sample 200mg in the crystal reaction tube of internal diameter 3mm, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then at 10%C3H8/H2It is warming up to 700 DEG C with 1 DEG C/min of heating rate from 400 DEG C under (volume fraction) atmosphere and keeps 2 hours, then under this reducing atmosphere, it is rapidly cooled to room temperature, obtain the composite of GDC-chromium carbide, its GDC size of high power scanning electron microscopic observation is about 20nm, and chromium carbide size is about 20nm.
Embodiment 6
(1) it is that 90:10 ratio accurately weighs 1.72g (NH in nano ceramics and molybdenum-containing oxide mass ratio4)6Mo7O24·4H2O、7.8Ce(NO3)3·6H2O、2.1gGd(NO3)3·6H2O, adds deionized water and is sufficiently stirred for until dissolving, obtain solution A;
(2) weigh 31.5g polyacrylic acid, add deionized water and be sufficiently stirred for until dissolving, obtain solution B;
(3) above-mentioned solution B is slowly added in solution A, and is 1 with concentrated nitric acid adjustment pH value, heat slow evaporation solution;
(4) to be heated be evaporated to formation colloidal sol after pour in evaporating dish, form composite oxide of metal just powder with heating by electric cooker burning;
(5) cerium oxide (GDC) and the molybdenum oxide (MoO3) of the doping of nano ceramics Gadolinia. and YSZ:MoO are obtained at 800 DEG C after being calcined 2 hours by first powder3Mass ratio 90:10;
(6) the sample tabletting after calcining being pulverized and sieved, taking 60～80 order sample 200mg in the crystal reaction tube of internal diameter 3mm, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then at 20%CH4/H2It is warming up to 900 DEG C with 2 DEG C/min of heating rates from 400 DEG C under (volume fraction) atmosphere and keeps 1 hour, then under this reducing atmosphere, it is rapidly cooled to room temperature, obtain the composite of GDC-molybdenum carbide, its YSZ size of high power scanning electron microscopic observation is about 50nm, and molybdenum carbide size is about 5nm.
Claims (8)
1. the synthetic method of a nano ceramics and nano-carbide composite, it is characterised in that: specifically comprise the following steps that
(1) weighing the slaine of nano ceramics and the presoma of nano-carbide, adding water is sufficiently stirred for dissolving and obtains solution A;
(2) weigh chelating agent to add water stirring and dissolving, obtain solution B;
(3) solution B is slowly added in solution A, continues stirring and solution heating evaporation is formed colloidal sol;
(4) pouring in evaporating dish by colloidal sol, heating by electric cooker burning obtains tungstenic, chromium, molybdenum composite oxides just powder, then it is obtained nano ceramics and tungstenic, chromium, molybdenum oxide composite in 2 hours at 500～1000 DEG C of temperature lower calcinations;
(5) carry out temperature programmed reduction process under reducing atmosphere, and keep 1～50h, be then rapidly decreased to room temperature under a reducing atmosphere, obtain nano ceramics and nano-carbide composite.
2. the method for claim 1, it is characterized in that: the slaine of described nano ceramics is one or two or more kinds in Yttrium trinitrate, Lanthanum (III) nitrate, strontium nitrate, zirconium nitrate, cerous nitrate, Gadolinium trinitrate, cobalt nitrate or ferric nitrate, the precursor of described nano-carbide is one or two or more kinds in ammonium tungstate, ammonium molybdate, chromic nitrate; It is 10:1～1:10 that the proportioning of the slaine of described nano ceramics and the precursor of nano-carbide meets the composite oxides mass ratio of nano ceramics and tungstenic, chromium or molybdenum.
3. the method for claim 1, it is characterised in that: described chelating agent is the one in ethylenediaminetetraacetic acid, triethanolamine, tartaric acid, citric acid, ammonium citrate, oxalic acid, polyacrylic acid or more than two kinds.
4. method as claimed in claim 1 or 2, it is characterised in that: described nano ceramics is mainly the one in the zirconium oxide of stabilized with yttrium oxide (YSZ), the cerium oxide (GDC) of Gadolinia. doping, the cerium oxide (LDC) of lanthanum oxide doping, lanthanum-strontium ferro-cobalt (LSCF) etc. or more than two kinds; The oxide of tungstenic, chromium or molybdenum is mainly one or two or more kinds in tungsten oxide, chromium oxide, molybdenum oxide, lanthanum molybdate, Lanthanum Chromite etc.; Nano-carbide is mainly the one of tungsten carbide, chromium carbide, molybdenum carbide etc. or more than two kinds.
5. the method as described in claim 1 or 3, it is characterised in that: the mol ratio of the chelating agent adopted and metal ion total amount is 1:1～10:1.
6. the method for claim 1, it is characterised in that: described reducing atmosphere is volume fraction be 1～50% methane, ethane, propane, the gas of one or two or more kinds in the hydro carbons such as normal butane and hydrogen gaseous mixture.
7. the method for claim 1, it is characterised in that: the temperature of described Temperature Programmed Processes is 400～1000 DEG C, and heating rate is 0.5～10 DEG C/min.
8. the method for claim 1, it is characterised in that: described nano ceramics is with the composite of nano-carbide, and nano-carbide is of a size of 5nm～200nm.
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| CN108505320A (en) * | 2018-04-25 | 2018-09-07 | 东南大学 | Composite oxide coating and its preparation method and application |
| CN112591754A (en) * | 2020-12-25 | 2021-04-02 | 太原理工大学 | Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite |
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| CN1470478A (en) * | 2003-06-20 | 2004-01-28 | 上海大学 | Rare earth-doped srstrontium cerate nano crystal ceramic preparing method |
| CN1884088A (en) * | 2005-06-21 | 2006-12-27 | 浙江师范大学 | Technology for preparing ultrafine nano metal oxide materials |
| US20110212829A1 (en) * | 2005-08-11 | 2011-09-01 | Dimascio Felice | High surface area ceramic catalysts and the manufacture thereof |
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| CN1470478A (en) * | 2003-06-20 | 2004-01-28 | 上海大学 | Rare earth-doped srstrontium cerate nano crystal ceramic preparing method |
| CN1884088A (en) * | 2005-06-21 | 2006-12-27 | 浙江师范大学 | Technology for preparing ultrafine nano metal oxide materials |
| US20110212829A1 (en) * | 2005-08-11 | 2011-09-01 | Dimascio Felice | High surface area ceramic catalysts and the manufacture thereof |
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| CN108505320A (en) * | 2018-04-25 | 2018-09-07 | 东南大学 | Composite oxide coating and its preparation method and application |
| CN112591754A (en) * | 2020-12-25 | 2021-04-02 | 太原理工大学 | Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite |
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