CN105664987B - A kind of synthetic method of nano ceramics and nano-carbide composite - Google Patents
A kind of synthetic method of nano ceramics and nano-carbide composite Download PDFInfo
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- CN105664987B CN105664987B CN201410675780.XA CN201410675780A CN105664987B CN 105664987 B CN105664987 B CN 105664987B CN 201410675780 A CN201410675780 A CN 201410675780A CN 105664987 B CN105664987 B CN 105664987B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 6
- 238000011946 reduction process Methods 0.000 claims abstract description 3
- 230000003247 decreasing effect Effects 0.000 claims abstract 2
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 claims description 8
- 229910003470 tongbaite Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 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 6
- 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 6
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 5
- 229910039444 MoC Inorganic materials 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 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
- 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000002243 precursor Substances 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
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-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
- 229910000423 chromium oxide Inorganic materials 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
- 229960001484 edetic acid Drugs 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
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 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 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001294 propane Substances 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
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001722 carbon compounds Chemical class 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- HKRXOWGILGJWPT-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O-2].[Y+3].[Zr+4] HKRXOWGILGJWPT-UHFFFAOYSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 239000002905 metal composite material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 229910003101 Y(NO3)3·6H2O Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002287 La2Mo2O9 Inorganic materials 0.000 description 2
- 229910002262 LaCrO3 Inorganic materials 0.000 description 2
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical class CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- -1 chromium Oxide Lanthanum Chromite Chemical compound 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 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 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 2
- 229910002617 Gd(NO3)3·6H2O 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
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction 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
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- SCJGVKYSOPVNSS-UHFFFAOYSA-N lanthanum;oxomolybdenum Chemical compound [La].[Mo]=O SCJGVKYSOPVNSS-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- NYWITVDHYCKDAU-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O--].[O--].[Y+3].[Zr+4] NYWITVDHYCKDAU-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the synthetic method of a kind of nano ceramics and nano-carbide composite.Specific steps include：Metal salt is weighed, dissolving is sufficiently stirred and obtains solution A；Weigh complexing agent and add water stirring and dissolving, obtain solution B；Solution B is slowly added into solution A, continues stirring and solution heating evaporation is formed into colloidal sol；Colloidal sol is poured into evaporating dish, heating burning obtains tungstenic, chromium, molybdenum composite oxides just powder, and it then is obtained into nano ceramics and tungstenic, chromium, molybdenum oxide composite in 500~1000 DEG C of temperature lower calcinations；Temperature programmed reduction process is carried out under reducing atmosphere, and keeps 1~50h, is then rapidly decreased to room temperature under a reducing atmosphere, is obtained nano ceramics and nano-carbide composite.The method by the addition of nano ceramics can effective stable carbide, and carbide size can be control effectively in several nanometers to hundreds of nanometers with metal proportioning is changed.
Description
Technical field
The invention belongs to field of nanometer technology, and in particular to the conjunction of a kind of nano ceramics and nano-carbide composite
Into method.
Technical background
Carbide is a kind of with compound is filled between metal-like properties, i.e. the carbon atom of small volume occupies metallic atom
The space of closs packing layer, formation have simple crystal structure.Carbide has unique electronic structure and superficiality because of it
Matter, the catalytic performance of class noble metal can be shown in catalytic reaction.Be mainly used in hydrogenation/dehydrogenation reaction, hydrodesulfurization/
Hydrodenitrogeneration reaction, the synthesis of ammonia and decomposition reaction energy (such as tungsten carbide, molybdenum carbide), it is that people study replacement precious metal material
Important research direction；In addition, carbide or one kind have very high fusing point and hardness, high heat endurance and machinery steady
It is qualitative, at room temperature almost resistance to various chemical attacks the features such as material, therefore be widely used in machine cut, mineral are opened
Adopt, manufacture the fields such as wear-resistant and high-temperature component and nuclear reactor (such as chromium carbide, zirconium carbide).At present, carbide is prepared
Method mainly includes：Direct carborization, self-propagating high-temperature synthesis, high-energy ball milling method, temperature programming carbonizatin method etc..Wherein, journey
Sequence heating carbonizatin method is simple to operate, the advantages that controllability is strong and be widely used.But the carbonization that all preparation methods obtain
Thing size is all unmanageable, and size is easy to loss of activity generally in micron order in catalytic reaction.In addition, current research
Person lacks the research on its catalytic performance influence of carbide size controllable pair.
The content of the invention
In view of the above-mentioned problems, the present invention provides a kind of synthetic method of nano ceramics and nano-carbide composite.Should
Method by the addition of nano ceramics can effective stable carbide, and carbide size can be existed with metal proportioning is changed
Several nanometers control effectively to hundreds of nanometers.And the interfacial effect of nano-carbide and nano ceramics has to catalytic activity
Have a major impact.
The present invention adopts the following technical scheme that realization：A kind of synthesis side of nano ceramics and nano-carbide composite
Method, comprise the following steps：
(1) metal salt of nano ceramics and the presoma of nano-carbide are weighed, adds water to be sufficiently stirred dissolving and obtains solution
A；
(2) weigh complexing agent and add water stirring and dissolving, obtain solution B；
(3) solution B is slowly added into solution A, continues stirring and solution heating evaporation is formed into colloidal sol；
(4) colloidal sol is poured into evaporating dish, electric furnace heating burning obtains tungstenic, chromium, molybdenum composite oxides just powder, then will
It obtains nano ceramics and tungstenic, chromium, molybdenum oxide composite in 2 hours in 500~1000 DEG C of temperature lower calcinations；
(5) temperature programmed reduction process is carried out under reducing atmosphere, and keeps 1~50h, it is then rapid under a reducing atmosphere
Room temperature is down to, obtains nano ceramics and nano-carbide composite.
The metal salt of described nano ceramics is yttrium nitrate, lanthanum nitrate, strontium nitrate, zirconium nitrate, cerous nitrate, gadolinium nitrate, nitre
One or two or more kinds in sour cobalt or ferric nitrate, the precursor of described nano-carbide is ammonium tungstate, ammonium molybdate, chromic nitrate
In one or two or more kinds；The proportioning of the metal salt of the nano ceramics and the precursor of nano-carbide meets nano ceramics
Composite oxides mass ratio with tungstenic, chromium or molybdenum is 10:1~1:10.
Described complexing agent is ethylenediamine tetra-acetic acid, triethanolamine, tartaric acid, citric acid, ammonium citrate, oxalic acid, poly- third
Olefin(e) acid etc. it is one or two kinds of more than, the mol ratio of complexing agent and metal ion total amount is 1：1~10：1.
Described nano ceramics be mainly stabilized with yttrium oxide zirconium oxide (YSZ), aoxidize Gd2 O3 cerium oxide (GDC),
More than the cerium oxide (LDC) of lanthanum oxide doping, lanthanum-strontium ferro-cobalt (LSCF) etc. are one or two kinds of；Tungstenic, chromium, molybdenum oxide are main
It is the one or more of tungsten oxide, chromium oxide, molybdenum oxide, lanthanum molybdate, Lanthanum Chromite etc.；Nano-carbide is mainly carbonized
Tungsten, chromium carbide, molybdenum carbide etc. it is one or two kinds of more than.
Described reducing atmosphere be volume fraction be 1~50% methane, ethane, propane, one kind of the hydro carbons such as normal butane
Or the gas of the kind above and the gaseous mixture of 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.
In described nano ceramics and the composite of nano-carbide, the size of nano-carbide is 5nm~200nm.
The present invention is had the following advantages relative to prior art and effect：
(1) powder at the beginning of a kind of method synthesized altogether by collosol and gel obtains tungstenic, chromium, molybdenum composite oxides, then by it
Nano ceramics and tungstenic, chromium, molybdenum oxide material are obtained in 500~1000 DEG C of temperature lower calcinations, passes through temperature-programmed reduction method
Selective carbonization is carried out, obtains nano ceramics and nano-carbide composite.
(2) the method by the addition of nano ceramics can effective stable carbide, and can with metal proportioning is changed
Carbide size is control effectively in several nanometers to hundreds of nanometers.
(3) while carbide size is adjusted, both contacts area, interfacial effect enhancing catalytic performance are increased.
Embodiment
The present invention is described in further detail with reference to embodiments, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) it is 40 by nano ceramics and chromium-containing oxide mass ratio:60 ratios accurately weigh 10.5g La (NO3)3·
6H2O、10g Cr(NO3)3·9H2O、2g Y(NO3)3·6H2O、12gZr(NO3)4·5H2O, add deionized water and be sufficiently stirred
Until dissolving, obtains solution A；
(2) 16.5g ethylenediamine tetra-acetic acids are weighed, deionized water is added and is sufficiently stirred until dissolving, obtains solution B；
(3) above-mentioned solution B is slowly added into solution A, and is 2 with concentrated nitric acid regulation pH value, heating slow evaporation is molten
Liquid；
(4) it is to be heated be evaporated to form colloidal sol after pour into evaporating dish, electricity consumption stove heat burn to be formed metal composite oxidation
The first powder of thing；
(5) zirconium oxide (YSZ) of nano ceramics stabilized with yttrium oxide is obtained after first powder is calcined 2 hours at 500 DEG C and containing chromium
Oxide Lanthanum Chromite (LaCrO3), and YSZ:LaCrO3Mass ratio 40:60；
(6) the sample tabletting after calcining is crushed and sieved, take 60~80 mesh sample 200mg anti-in internal diameter 3mm quartz
Ying Guanzhong, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then in 20%CH4/H2With 1 DEG C/min of heating under (volume fraction) atmosphere
Speed is warming up to 600 DEG C from 400 DEG C and kept for 4 hours, is then rapidly cooled to room temperature under this reducing atmosphere, obtains YSZ- carbon
Change the composite of chromium, 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 70 by nano ceramics and molybdenum-containing oxide mass ratio:30 ratios accurately weigh 4.2gLa (NO3)3·6H2O、
1.72g(NH4)6Mo7O24·4H2O、3.26g Y(NO3)3·6H2O、21.1gZr(NO3)4·5H2O, it is abundant to add deionized water
Stirring obtains solution A until dissolving；
(2) 31.5g polyacrylic acid is weighed, deionized water is added and is sufficiently stirred until dissolving, obtains solution B；
(3) above-mentioned solution B is slowly added into solution A, and is 2 with concentrated nitric acid regulation pH value, heating slow evaporation is molten
Liquid；
(4) it is to be heated be evaporated to form colloidal sol after pour into evaporating dish, electricity consumption stove heat burn to be formed metal composite oxidation
The first powder of thing；
(5) zirconium oxide (YSZ) of nano ceramics stabilized with yttrium oxide is obtained after first powder is calcined 2 hours at 800 DEG C and containing molybdenum
Oxide lanthanum molybdate (La2Mo2O9), and YSZ:La2Mo2O9Mass ratio 70:30；
(6) the sample tabletting after calcining is crushed and sieved, take 60~80 mesh sample 200mg anti-in internal diameter 3mm quartz
Ying Guanzhong, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then in 20%CH4/H2With 2 DEG C/min of heatings under (volume fraction) atmosphere
Speed is warming up to 800 DEG C from 400 DEG C and kept for 2 hours, is then rapidly cooled to room temperature under this reducing atmosphere, obtains YSZ- carbon
Change the composite of molybdenum, its YSZ size of high power scanning electron microscopic observation is about 20nm, and molybdenum carbide size is about 10nm.
Embodiment 3
(1) it is 50 by nano ceramics and tungstenic oxide mass ratio:50 ratios accurately weigh 4.24g (NH4)10W12O41·
4H2O、2.35g Y(NO3)3·6H2O、14.9g Zr(NO3)4·5H2O, add deionized water and be sufficiently stirred until dissolving, is obtained
Solution A；
(2) 37.5g ammonium citrates are weighed, deionized water is added and is sufficiently stirred until dissolving, obtains solution B；
(3) above-mentioned solution B is slowly added into solution A, and is 3 with concentrated nitric acid regulation pH value, heating slow evaporation is molten
Liquid；
(4) it is to be heated be evaporated to form colloidal sol after pour into evaporating dish, electricity consumption stove heat burn to be formed metal composite oxidation
The first powder of thing；
(5) zirconium oxide (YSZ) and the oxidation of nano ceramics stabilized with yttrium oxide are obtained after first powder is calcined 2 hours at 700 DEG C
Tungsten (WO3), and YSZ:WO3Mass ratio 50:50；
(6) the sample tabletting after calcining is crushed and sieved, take 60~80 mesh sample 200mg anti-in internal diameter 3mm quartz
Ying Guanzhong, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then in 5%C4H10/H2Risen under (volume fraction) atmosphere with 5 DEG C/min
Warm speed is warming up to 700 DEG C from 400 DEG C and kept for 8 hours, is then rapidly cooled to room temperature under this reducing atmosphere, obtains YSZ-
The composite of 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 80 by nano ceramics and chromium-containing oxide mass ratio:20 ratios accurately weigh 10gCr (NO3)3·9H2O、
3.73g Y(NO3)3·6H2O、24.2g Zr(NO3)4·5H2O, add deionized water and be sufficiently stirred until dissolving, obtains solution
A；
(2) 20.1g citric acids are weighed, deionized water is added and is sufficiently stirred until dissolving, obtains solution B；
(3) above-mentioned solution B is slowly added into solution A, and is 4 with concentrated nitric acid regulation pH value, heating slow evaporation is molten
Liquid；
(4) it is to be heated be evaporated to form colloidal sol after pour into evaporating dish, electricity consumption stove heat burn to be formed metal composite oxidation
The first powder of thing；
(5) zirconium oxide (YSZ) and the oxidation of nano ceramics stabilized with yttrium oxide are obtained after first powder is calcined 2 hours at 900 DEG C
Chromium (Cr2O3), and YSZ:Cr2O3Mass ratio 80:20；
(6) the sample tabletting after calcining is crushed and sieved, take 60~80 mesh sample 200mg anti-in internal diameter 3mm quartz
Ying Guanzhong, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then in 20%CH4/H2With 2 DEG C/min of heatings under (volume fraction) atmosphere
Speed is warming up to 900 DEG C from 400 DEG C and kept for 2 hours, is then rapidly cooled to room temperature under this reducing atmosphere, obtain YSZ-
The composite of 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 40 by nano ceramics and chromium-containing oxide mass ratio:60 ratios accurately weigh 10.5g La (NO3)3·
6H2O、10g Cr(NO3)3·9H2O、7.8Ce(NO3)3·6H2O、2.1gGd(NO3)3·6H2O, add deionized water and fully stir
Mix until dissolving, obtains solution A；
(2) 20.4g ethylenediamine tetra-acetic acids are weighed, deionized water is added and is sufficiently stirred until dissolving, obtains solution B；
(3) above-mentioned solution B is slowly added into solution A, and is 2 with concentrated nitric acid regulation pH value, heating slow evaporation is molten
Liquid；
(4) it is to be heated be evaporated to form colloidal sol after pour into evaporating dish, electricity consumption stove heat burn to be formed metal composite oxidation
The first powder of thing；
(5) cerium oxide (GDC) of nano ceramics oxidation Gd2 O3 is obtained after first powder is calcined 2 hours at 500 DEG C and containing chromium
Oxide Lanthanum Chromite (LaCrO3), and GDC:LaCrO3Mass ratio 40:60；
(6) the sample tabletting after calcining is crushed and sieved, take 60~80 mesh sample 200mg anti-in internal diameter 3mm quartz
Ying Guanzhong, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then in 10%C3H8/H2Risen under (volume fraction) atmosphere with 1 DEG C/min
Warm speed is warming up to 700 DEG C from 400 DEG C and kept for 2 hours, is then rapidly cooled to room temperature under this reducing atmosphere, obtains GDC-
The composite of 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 90 by nano ceramics and molybdenum-containing oxide mass ratio:10 ratios accurately weigh 1.72g (NH4)6Mo7O24·
4H2O、7.8Ce(NO3)3·6H2O、2.1g Gd(NO3)3·6H2O, add deionized water and be sufficiently stirred until dissolving, is obtained molten
Liquid A；
(2) 31.5g polyacrylic acid is weighed, deionized water is added and is sufficiently stirred until dissolving, obtains solution B；
(3) above-mentioned solution B is slowly added into solution A, and is 1 with concentrated nitric acid regulation pH value, heating slow evaporation is molten
Liquid；
(4) it is to be heated be evaporated to form colloidal sol after pour into evaporating dish, electricity consumption stove heat burn to be formed metal composite oxidation
The first powder of thing；
(5) cerium oxide (GDC) and the oxidation of nano ceramics oxidation Gd2 O3 are obtained after first powder is calcined 2 hours at 800 DEG C
Molybdenum (MoO3), and YSZ:MoO3Mass ratio 90:10；
(6) the sample tabletting after calcining is crushed and sieved, take 60~80 mesh sample 200mg anti-in internal diameter 3mm quartz
Ying Guanzhong, lower 200 DEG C of nitrogen atmosphere purges 1 hour, then in 20%CH4/H2With 2 DEG C/min of heatings under (volume fraction) atmosphere
Speed is warming up to 900 DEG C from 400 DEG C and kept for 1 hour, is then rapidly cooled to room temperature under this reducing atmosphere, obtains GDC- carbon
Change the composite of molybdenum, its YSZ size of high power scanning electron microscopic observation is about 50nm, and molybdenum carbide size is about 5nm.
Claims (6)
- A kind of 1. synthetic method of nano ceramics and nano-carbide composite, it is characterised in that：Comprise the following steps that：(1) metal salt of nano ceramics and the presoma of nano-carbide are weighed, adds water to be sufficiently stirred dissolving and obtains solution A, institute The metal salt for the nano ceramics stated is yttrium nitrate, lanthanum nitrate, strontium nitrate, zirconium nitrate, cerous nitrate, gadolinium nitrate, cobalt nitrate or nitric acid One or two or more kinds in iron, the precursor of described nano-carbide is ammonium tungstate, ammonium molybdate, one kind in chromic nitrate or More than two kinds；(2) weigh complexing agent and add water stirring and dissolving, obtain solution B, described complexing agent be ethylenediamine tetra-acetic acid, triethanolamine, One kind in tartaric acid, citric acid, ammonium citrate, oxalic acid, polyacrylic acid or more than two kinds；(3) solution B is slowly added into solution A, continues stirring and solution heating evaporation is formed into colloidal sol；(4) colloidal sol is poured into evaporating dish, electric furnace heating burning obtain tungstenic, chromium, molybdenum composite oxides just powder, then by its 500~1000 DEG C of temperature lower calcinations obtain nano ceramics and tungstenic, chromium, molybdenum oxide composite in 2 hours；(5) temperature programmed reduction process is carried out under reducing atmosphere, and keeps 1~50h, is then rapidly decreased under a reducing atmosphere Room temperature, obtains nano ceramics and nano-carbide composite, and described reducing atmosphere is the first that volume fraction is 1~50% The gaseous mixture of one or two or more kinds of gas and hydrogen in alkane, ethane, propane, normal butane.
- 2. the method as described in claim 1, it is characterised in that：The metal salt of the nano ceramics and the preceding body of nano-carbide It is 10 that the proportioning of body, which meets nano ceramics and the composite oxides mass ratio of tungstenic, chromium or molybdenum,:1~1:10.
- 3. the method as described in claim 1, it is characterised in that：Described nano ceramics is mainly the oxidation of stabilized with yttrium oxide Zirconium, the oxidation cerium oxide of Gd2 O3, the cerium oxide of lanthanum oxide doping, one kind in lanthanum-strontium ferro-cobalt or more than two kinds；Tungstenic, chromium Or the oxide of molybdenum is mainly the one or two or more kinds in tungsten oxide, chromium oxide, molybdenum oxide, lanthanum molybdate, Lanthanum Chromite；Nano-sized carbon Compound is mainly tungsten carbide, chromium carbide, one kind of molybdenum carbide or more than two kinds.
- 4. the method as described in claim 1, it is characterised in that：Used complexing agent and the mol ratio of metal ion total amount are 1：1~10：1.
- 5. the method as described in claim 1, it is characterised in that：The temperature of described Temperature Programmed Processes is 400~1000 DEG C, Heating rate is 0.5~10 DEG C/min.
- 6. the method as described in claim 1, it is characterised in that：Described nano ceramics and the composite of nano-carbide In, the size of nano-carbide is 5nm~200nm.
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