CN106391094B - The preparation method of the composite material of the silica supported nanometer MoO3 of mesoporous carbon-and nano-metal particle - Google Patents
The preparation method of the composite material of the silica supported nanometer MoO3 of mesoporous carbon-and nano-metal particle Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 43
- 239000002923 metal particle Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 235000019441 ethanol Nutrition 0.000 claims description 31
- 239000011343 solid material Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 239000011833 salt mixture Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 25
- 239000011148 porous material Substances 0.000 abstract description 20
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 15
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000012546 transfer Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000009833 condensation Methods 0.000 description 14
- 230000005494 condensation Effects 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021435 silicon-carbon complex Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical class [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical class OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- -1 aromatic nitro compounds Chemical class 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000011944 chemoselective reduction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011867 silicon-carbon complex material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of silica supported nanometer MoO of mesoporous carbon-3With the preparation method of the composite material of nano-metal particle, the high specific surface area and mesoporous MoO of fragrant nitro compound selectivity hydrogen transfer reduction can be used for3- Ni (Co, Fe)/NG-C@SBA-15 catalyst, preparation method of the present invention prepare catalyst by pyrolysis reduction method after simple double-steeping, and the preparation method process equipment is simple, it is easy to operate, the mesoporous MoO with narrow pore size distribution and high-specific surface area can be made3- Ni (Co, Fe)/NG-C@SBA-15 composite materials, the catalyst have high activity and selectivity for the selective hydrogen transfer reduction of industrial common a variety of fragrant nitro compounds.
Description
Technical field
The present invention relates to a kind of preparation methods of composite catalyst, negative more particularly to a kind of mesoporous carbon-silica
Nano composite catalyst is carried, technical field of inorganic nano-material preparation is applied to.
Background technology
According to international pure and applied chemistry association（IUPAC）Definition, porous material can be according to their bore dias
Size is divided into three classes：Material of the aperture less than 2 nm is poromerics（microporous materials）；Aperture is in 2-50
The material of nm is mesopore material（mesoporous materials）；Material of the aperture more than 50 nm is large pore material
（macroporous materials）.Mesoporous material has high specific surface area, good pore passage structure, narrow aperture
The features such as distribution, continuously adjustable pore size so that it is used widely in absorption, separation and catalysis.
Mesopore silicon oxide (SiO2) there is higher specific surface area, it is easy to prepare, it is cheap, and carried as catalyst
When body, unique porous structure is also beneficial to the mass transfer in reaction process and heat transfer.The high catalytic activity of nickel, cobalt and iron and
Its economic serviceability makes it be widely used in various catalysis reaction.As a kind of transition elements, the addition energy of molybdenum
Enough improve nickel, cobalt and reduces nanoparticle size at the metal nanoparticles such as iron dispersion degree, to improve the activity of catalyst with
Selectivity and stability, carbon/silica composite have huge potential in numerous areas such as chemistry, materialogy, environmentologys
Application prospect.
Zhongkui Zhao et al. are in Cobalt-modified molybdenum carbide as an
efficient catalyst for chemoselective reduction of aromatic nitro compounds.
Green Chemistry（Green Chemistry）In 2014,16,1274-1281. mono- texts, by CH4In H2Gaseous mixture restores
By the Mo by cobalt modification2C is carried on activated carbon, and the catalyst prepared turns the selective hydrogen of fragrant nitro compound
Moving reaction has very high activity.Chengjun Jiang et al. are in Chemoselective Transfer
Hydrogenation of Nitroarenes Catalyzed by Highly Dispersed, Supported Nickel
Nanoparticles. ACS Catalysis in 2015,5,4,814 4818. one texts, are prepared by atomic layer deposition method
Tiny nano particle nickel load on silica for the selective hydrogen transfer reaction of fragrant nitro compound have higher activity.
The most preparation process of catalyst of document report is complex, is awkward or specific surface area is smaller, aperture point
Cloth is not concentrated, and transmission of the substance in its duct in reaction process is unfavorable for, while acting on fragrant nitro compound hydrogen migration
Catalytic rate is slower.Thus develop a kind of easy to operate, processing is convenient, and reaction condition is mild, and raw material is easy to get, it is of low cost still
The match in excellence or beauty non-metallic catalyst of even more than noble metal catalyst of catalytic activity and selection performance is used for fragrant nitro compound hydrogen and turns
Moving reaction method for preparing becomes technical problem urgently to be resolved hurrily.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The silica supported nanometer MoO of mesoporous carbon-3With the preparation method of the composite material of nano-metal particle, a kind of high-ratio surface is prepared
The mesoporous NG-C of product indicates the graphite structure carbon (MoO containing N doping in carbon species3- Ni (Co, Fe)/NG-C@SBA-15) it is multiple
Condensation material, simple, easy to operate, the prepared MoO of preparation method process equipment of the present invention3-Ni(Co, Fe)/NG-C@SBA-
It is mesoporous with high-specific surface area that there is 15 composite materials narrow pore size to be distributed, and preparation process equipment is simple, easy to operate, active
It is high.
Purpose is created to reach foregoing invention, the present invention uses following technical proposals：
A kind of silica supported nanometer MoO of mesoporous carbon-3With the preparation method of the composite material of nano-metal particle, including
Following steps：
A. using the mixed solution of second alcohol and water as solvent, by a certain amount of soluble inorganic metal salt, ammonium molybdate and
SBA-15 is dissolved in the mixed solution of water and ethyl alcohol, soluble inorganic metal salt, ammonium molybdate and SBA-15 addition quality
Than for（0.03~0.06）：（0.03~0.12）：1, sonic oscillation at least 30 minutes at room temperature, until SBA-15 is completely dispersed
In mixed solution, the first mixed solution is obtained；Soluble inorganic metal salt preferably uses arbitrary in nickel salt, cobalt salt and molysite
A kind of salt or arbitrary several salt-mixture；Soluble inorganic metal salt preferably uses nitrate；Soluble inorganic metal salt is more excellent
Choosing is using Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and any one salt in six nitric hydrate iron or arbitrary several mixing
Salt；When the mixed solution of second alcohol and water is as solvent, the mixed volume ratio of preferred alcohol and water（v/v）It is 1：（1~3）； b.
The first mixed solution prepared in the step a is stirred continuously at 40-60 DEG C, gradual solvent evaporated will obtain
Solid heats at least 2 h at a temperature of not higher than 400 DEG C, obtains the first solid material under air atmosphere；
C. using the mixed solution of second alcohol and water as solvent, the first solid material obtained by the step b is dissolved in second
In the mixed solution of alcohol and water, it is molten then to weigh the mixing that a certain amount of hydration 1.10- ferrosins are also added to second alcohol and water
It is dissolved in liquid, the mass ratio of the addition of the first solid material and a hydration 1.10- ferrosins is 1：（0.2~1.2）, then
It is stirred continuously mixed solution at 40-60 DEG C, until gradually solvent evaporated, obtains the second solid material；The mixing of second alcohol and water is molten
When liquid is as solvent, the mixed volume ratio of preferred alcohol and water（v/v）It is 1：（1~3）；
D. the second solid material of the gained in the step c is warming up to the heating rate for being not less than 5 DEG C/min
800 DEG C of calcination temperature then under 800 DEG C of calcination temperature, and roasts at least 2 h, prepares mesoporous in a nitrogen atmosphere
The silica supported nanometer MoO of carbon-3With the composite material of nano-metal particle.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention uses nanometer casting mold-pyrolysismethod, this method to control nickel（Cobalt or iron）With the addition of molybdenum, avoid
The formation of bulky grain nano-particle in preparation process, to influencing activity；
2. the present invention uses and first inorganic salts is carried in mesoporous SBA-15 duct, then impregnates organic nitrogen
It closes object and obtains metal nanoparticle nickel by way of pyrolysis（Cobalt or iron）It is carried on carbon silicon complex carrier, remains with molybdenum
SBA-15 narrow pore sizes are distributed and the property of high-specific surface area, obtain the catalyst with high activity and stability；
3. the mesoporous MoO that the present invention synthesizes high-specific surface area, has narrow pore size to be distributed3-Ni(Co,Fe)/NG-C@
SBA-15 composite materials, solvent used in simultaneous reactions is deionized water and ethyl alcohol has that easy to operate, process equipment is simple
Single advantage, while material price is cheap, is easy to get；
4. the hydrogen transfer reduction that catalyst of the present invention is applied to industrial common fragrant nitro compound shows high work
Property and selectivity, and reaction condition is mild, it is easy to operate.
Description of the drawings
Fig. 1 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention one3With answering for nano-metal particle
The X-ray powder diffraction of condensation material（XRD）The structure chart of acquisition.
Fig. 2 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention one3With answering for nano-metal particle
The high power transmission electron microscope TEM pictures of condensation material.
Fig. 3 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention one3With answering for nano-metal particle
The nitrogen adsorption desorption and graph of pore diameter distribution of condensation material.
Fig. 4 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention two3With answering for nano-metal particle
The X-ray powder diffraction of condensation material（XRD）The structure chart of acquisition.
Fig. 5 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention two3With answering for nano-metal particle
The high power transmission electron microscope TEM pictures of condensation material.
Fig. 6 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention two3With answering for nano-metal particle
The nitrogen adsorption desorption and graph of pore diameter distribution of condensation material.
Fig. 7 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention three3With answering for nano-metal particle
The X-ray powder diffraction of condensation material（XRD）The structure chart of acquisition.
Fig. 8 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention three3With answering for nano-metal particle
The high power transmission electron microscope TEM pictures of condensation material.
Fig. 9 is the silica supported nanometer MoO of mesoporous carbon-prepared by the embodiment of the present invention three3With answering for nano-metal particle
The nitrogen adsorption desorption and graph of pore diameter distribution of condensation material.
Specific implementation mode
Details are as follows for the preferred embodiment of the present invention：
Embodiment one：
In the present embodiment, referring to Fig. 1~3, a kind of silica supported nanometer MoO of mesoporous carbon-3With nano-metal particle
The preparation method of composite material, which is characterized in that include the following steps：
A. using the mixed solution of second alcohol and water as solvent, by 0.3g Nickelous nitrate hexahydrates, tetra- molybdic acid hydrates of 0.0334g
Ammonium and 1g SBA-15 are dissolved in 40ml water/ethyl alcohol (v/v=1:1) in mixed solution, sonic oscillation 30 minutes at room temperature, until
SBA-15 is completely dispersed in the solution, obtains the first mixed solution；
B. the first mixed solution prepared in the step a is stirred continuously at 40 DEG C, is gradually evaporated molten
Agent obtains solid under air atmosphere, and 400 DEG C of 2 h of heat treatment obtain the first solid material；
C. using the mixed solution of second alcohol and water as solvent, the first solid material 0.5g obtained by the step b is molten
In 40ml volume ratios be 1：3 water, alcohol mixed solution then weigh 0.8g mono- and are hydrated 1.10- ferrosins, exist after mixing
It is stirred continuously at 40 DEG C, gradually solvent evaporated, obtains the second solid material；
D. the second solid material of the gained in the step c is warming up to 800 DEG C with the heating rate of 5 DEG C/min
Calcination temperature then under 800 DEG C of calcination temperature, and roasts 2 h, prepares composite mesoporous oxidation of coal in a nitrogen atmosphere
Silicon composite.
Experimental test and analysis：
The project of detection and its instrument used are as follows：
N is carried out to gained sample2Adsorption/desorption measures, and measures the BET specific surface area and pore-size distribution of material；It is used
Instrument is Micromeritics companies of U.S. ASAP2020 automatically quick specific surface area and pore size distribution determining instrument, referring to figure
3；Sample need to deaerate 8h at 250 DEG C, slough the other materials of moisture and physical absorption；Sample is in Rigaku D/max-2550 X
X ray diffractometer x carries out XRD spectrum measurement, to determine the obtained target product of experiment and purity, referring to Fig. 1.Determination condition is
CuKa（l=1.5406Å）, 40KV, 100mA, Scan speed：0.02°/s；Transmission electron microscope photo instrument is JEM-2010F
Microscope, 200 kV of accelerating potential, referring to Fig. 2.
Accurately weigh the silica supported nanometer MoO of 5mg mesoporous carbons-manufactured in the present embodiment3With answering for nano-metal particle
Condensation material is scattered in as catalyst in 6ml ethanol solutions, and 6mmol nitro compounds and 48mmol hydrations is being added
Hydrazine reacts 15-25 minutes in 100 C water baths after sealing, takes out and cooled down with a large amount of cold water immediately after, after reaction
Sample with liquid chromatogram GC-3800 analyze quantitative.
Analysis test is carried out to composite mesoporous silicon oxide carbide composite material manufactured in the present embodiment, it will be mesoporous obtained by this example
Composite carbon silica composite material carries out XRD spectrum measurement, and transmission electron microscope (TEM) measures and N2 suctions-desorption measures.Figure
1 is the XRD diagram of composite mesoporous silicon oxide carbide composite material obtained by this example, it can be seen from figure 1 that having in the XRD diagram of counter sample
The diffraction maximum of SiO2 and Ni, but in figure, without apparent MoO3Corresponding diffraction maximum, XRD spectrum show MoO3Particle uniformly divides
It is dispersed in silica and carbon complex.Fig. 2 is that composite mesoporous silicon oxide carbide composite material high power transmitted electron obtained by this example is aobvious
Micro mirror TEM pictures, figure it is seen that Ni even particulate dispersions are on mesopore silicon oxide/carbon complex carrier.The built-in figure of Fig. 3
It is composite mesoporous silicon oxide carbide composite material pore size distribution curve and N obtained by this example2Suction-desorption isothermal curve.Pore size distribution is bent
Line is mapped to aperture once differentiation with Kong Rong, and ordinate should be dV/dr, unit cm-3.g-1.nm-1, Kong Rong is represented with aperture
Change rate, abscissa are aperture, unit nm.Adsorption isotherm map, abscissa P/P0Opposite pressure is represented, is dimensionless number
Value, P is the absolute pressure of test point nitrogen, P0It is the saturated vapour pressure of nitrogen under test temperature, the suction of opposite pressure, that is, nitrogen
Attached equilibrium pressure is relative to its saturated vapour pressure size；Ordinate is adsorbance, is to have dimension numerical value, and unit quantity is inhaled when referring to balance
The amount of the attached dose of adsorbate adsorbed under equilibrium temperature and pressure.The amount of adsorbent is measured in mass, and the amount of adsorbate is then with body
Product, the gauge amount of quality or substance, but with adsorbate, gas volume measures under the status of criterion (STP) mostly, therefore it is common
Unit dimension is cm3/ g or mL/g is indicated as being the status of criterion with STP thereafter.Mesoporous carbon-manufactured in the present embodiment is silica supported
Nanometer MoO3Composite material specific surface area with nano-metal particle is 550 m2/ g, average pore size are 4.0 nm, Kong Rongwei 0.50
Cm3/g, pore-size distribution are relatively uniform and narrow.Composite mesoporous silicon oxide carbide composite material obtained by this example as catalyst for
The hydrogen transfer reduction of industrial common fragrant nitro compound shows high activity and selectivity, while turn over number, substrate are used
Amount and catalyst amount are higher, effective for a variety of nitro compounds, and show higher stability, recycled for multiple times
Non-inactivation.As a result the number 1-11 in table 1 is seen.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, referring to Fig. 4~6, a kind of silica supported nanometer MoO of mesoporous carbon-3With nano-metal particle
The preparation method of composite material, which is characterized in that include the following steps：
A. using the mixed solution of second alcohol and water as solvent, by 0.3g cabaltous nitrate hexahydrates, tetra- molybdic acid hydrates of 0.0334g
Ammonium and 1g SBA-15 are dissolved in 40ml water/ethyl alcohol (v/v=1:1) in mixed solution, sonic oscillation 30 minutes at room temperature, until
SBA-15 is completely dispersed in the solution, obtains the first mixed solution；
B. the first mixed solution prepared in the step a is stirred continuously at 60 DEG C, is gradually evaporated molten
Agent obtains solid under air atmosphere, and 400 DEG C of 2 h of heat treatment obtain the first solid material；
C. it is 1 the first solid material 0.5g obtained by the step b to be dissolved in 40ml volume ratios：3 water, ethyl alcohol are mixed
Solution is closed, 0.8g mono- is then weighed and is hydrated 1.10- ferrosins, be stirred continuously at 60 DEG C after mixing, gradually solvent evaporated；
D. the second solid material of the gained in the step c is warming up to 800 DEG C with the heating rate of 5 DEG C/min
Calcination temperature then under 800 DEG C of calcination temperature, and roasts 2 h, prepares composite mesoporous oxidation of coal in a nitrogen atmosphere
Silicon composite.
Experimental test and analysis：
Accurately weigh the silica supported nanometer MoO of 5mg mesoporous carbons-manufactured in the present embodiment3With answering for nano-metal particle
Condensation material is scattered in as catalyst in 6ml ethanol solutions, and 6mmol nitro compounds and 48mmol hydrations is being added
Hydrazine reacts 15-25 minutes in 100 C water baths after sealing, takes out and cooled down with a large amount of cold water immediately after, after reaction
Sample with liquid chromatogram GC-3800 analyze quantitative.
The silica supported nanometer MoO of mesoporous carbon-manufactured in the present embodiment3It is penetrated with the X of the composite material of nano-metal particle
Line powder diffraction（XRD）The structure chart of acquisition, high power transmission electron microscope TEM pictures and pore size distribution curve and N2Inhale-
Isothermal curve is desorbed as shown in figures 4-6, the silica supported nanometer MoO of mesoporous carbon-manufactured in the present embodiment3With nano metal
The composite material specific surface area of grain is 590 m2/ g, average pore size are 4.0 nm, and hole holds 0.50cm3/g, and pore-size distribution is more equal
It is even narrow.The silica supported nanometer MoO of mesoporous carbon-manufactured in the present embodiment3It is used as and urges with the composite material of nano-metal particle
Agent shows high activity and the number 12 in selectivity such as table 1 for the hydrogen transfer reduction of nitro compound.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 7~9, a kind of silica supported nanometer MoO of mesoporous carbon-3With nano-metal particle
The preparation method of composite material, which is characterized in that include the following steps：
A. using the mixed solution of second alcohol and water as solvent, by six nitric hydrate iron of 0.25g, tetra- molybdic acid hydrates of 0.0334g
Ammonium and 1g SBA-15 are dissolved in 40ml water/ethyl alcohol (v/v=1:1) in mixed solution, sonic oscillation 30 minutes at room temperature, directly
It is completely dispersed in the solution to SBA-15, obtains the first mixed solution；
B. the first mixed solution prepared in the step a is stirred continuously at 50 DEG C, is gradually evaporated molten
Agent obtains solid under air atmosphere, and 400 DEG C of 2 h of heat treatment obtain the first solid material；
C. it is 1 the first solid material 0.5g obtained by the step b to be dissolved in 40ml volume ratios：3 water, ethyl alcohol are mixed
Solution is closed, 0.8g mono- is then weighed and is hydrated 1.10- ferrosins, be stirred continuously at 50 DEG C after mixing, gradually solvent evaporated；
D. the second solid material of the gained in the step c is warming up to 800 DEG C with the heating rate of 5 DEG C/min
Calcination temperature then under 800 DEG C of calcination temperature, and roasts 2 h, prepares composite mesoporous oxidation of coal in a nitrogen atmosphere
Silicon composite.
Experimental test and analysis：
Accurately weigh the silica supported nanometer MoO of 5mg mesoporous carbons-manufactured in the present embodiment3With answering for nano-metal particle
Condensation material is scattered in as catalyst in 6ml ethanol solutions, and 6mmol nitro compounds and 48mmol hydrations is being added
Hydrazine reacts 15-25 minutes in 100 C water baths after sealing, takes out and cooled down with a large amount of cold water immediately after, after reaction
Sample with liquid chromatogram GC-3800 analyze quantitative.
The silica supported nanometer MoO of mesoporous carbon-manufactured in the present embodiment3It is penetrated with the X of the composite material of nano-metal particle
Line powder diffraction（XRD）The structure chart of acquisition, high power transmission electron microscope TEM pictures and pore size distribution curve and N2Inhale-
Isothermal curve is desorbed as shown in figs. 7-9, the silica supported nanometer MoO of mesoporous carbon-manufactured in the present embodiment3With nano metal
The composite material specific surface area of grain is 590 m2/ g, average pore size are 4.0 nm, and hole holds 0.50cm3/ g, pore-size distribution are relatively uniform
It is narrow.The silica supported nanometer MoO of mesoporous carbon-manufactured in the present embodiment3Composite material with nano-metal particle is as catalysis
Agent shows high activity and the number 13 in selectivity such as table 1 for the hydrogen transfer reduction of nitro compound.
It is certain equipped in suitable ethanol solution retort, adding that above-described embodiment takes a certain amount of catalyst to be scattered in
The nitro compound of amount and appropriate hydrazine hydrate take rapidly after reacting a period of time in 100 degrees Celsius in the absence of air conditions
Go out, and analyzed with gas-chromatography GC-3800 after being cooled down immediately with cold water, compares the experimental result of above-described embodiment, referring to
Such as the following table 1.
The hydrogen of 1. embodiment of the present invention one of table, embodiment two and three catalyst of embodiment for the fragrant nitro compound in part
Shift reduction result contrast table
| Number | Catalyst | Reactant | Time（min） | Selectivity (%) | Yield (%) |
| 1 | Without catalyst | To this methyl ether of nitro | 15 | 0 | 0 |
| 2 | MoO3-Ni/NG-C@SBA-15 | To this methyl ether of nitro | 15 | 100 | 100 |
| 3 | MoO3-Ni/NG-C@SBA-15 | 4- nitrotoleunes | 15 | 100 | 100 |
| 4 | MoO3-Ni/NG-C@SBA-15 | 2- nitrotoleunes | 15 | 100 | 100 |
| 5 | MoO3-Ni/NG-C@SBA-15 | 2- chloronitrobenzenes | 15 | 98 | 100 |
| 6 | MoO3-Ni/NG-C@SBA-15 | 3- chloronitrobenzenes | 15 | 100 | 100 |
| 7 | MoO3-Ni/NG-C@SBA-15 | 2- chlorophenols | 25 | 100 | 100 |
| 8 | It recycles 1 time | To this methyl ether of nitro | 15 | 100 | 100 |
| 9 | It recycles 2 times | To this methyl ether of nitro | 15 | 100 | 100 |
| 10 | It recycles 3 times | To this methyl ether of nitro | 15 | 100 | 100 |
| 11 | It recycles 4 times | To this methyl ether of nitro | 15 | 100 | 100 |
| 12 | MoO3-Co/NG-C@SBA-15 | To this methyl ether of nitro | 7 | 98 | 100 |
| 13 | MoO3-Fe/NG-C@SBA-15 | To this methyl ether of nitro | 20 | 100 | 100 |
Above-described embodiment is prepared for high specific surface area and mesoporous MoO3- Ni (Co, Fe)/NG-C@SBA-15 carbon/silica is multiple
The preparation method and applications of mixture catalyst are reacted in the selective hydrogen transfer reduction of fragrant nitro compound.
The above embodiment of the present invention is prepared for ordered mesopore carbon/silica composite load nano-sized molybdenum oxide of N doping
With metallic nickel（Cobalt, iron）Particle is put into composite material, i.e. MoO3- Ni (Co, Fe)/NG-C@SBA-15, wherein NG indicates nitrogen member
The graphite structure of element doping, can be used for the fragrant nitro compound catalyst of hydrogen migration catalysis reduction, and the above embodiment of the present invention is logical
Pyrolysis reduction method prepares the silica supported nanometer MoO of mesoporous carbon-after crossing simple double-steeping3With answering for nano-metal particle
Condensation material, the preparation method process equipment is simple, easy to operate, can be made with narrow pore size distribution and high-specific surface area
Mesoporous MoO3- Ni (Co, Fe)/NG-C@SBA-15 composite materials, as the catalyst, for industrial common a variety of fragrant nitre
The selective hydrogen transfer reduction of based compound has high activity and selectivity.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Without departing from the silica supported nanometer MoO of mesoporous carbon-of the present invention3With the preparation method of the composite material of nano-metal particle
Technical principle and inventive concept, belong to protection scope of the present invention.
Claims (5)
1. a kind of silica supported nanometer MoO of mesoporous carbon-3With the preparation method of the composite material of nano-metal particle, feature exists
In including the following steps：
A. using the mixed solution of second alcohol and water as solvent, soluble inorganic metal salt uses appointing in nickel salt, cobalt salt and molysite
It anticipates a kind of salt or arbitrary several salt-mixture, a certain amount of soluble inorganic metal salt, ammonium molybdate and SBA-15 is dissolved in water
In the mixed solution of ethyl alcohol, soluble inorganic metal salt, ammonium molybdate and SBA-15 addition mass ratio be (0.03~
0.06)：(0.03~0.12)：1, sonic oscillation at least 30 minutes at room temperature, until SBA-15 is thoroughly dispersed in mixed solution
In, obtain the first mixed solution；
B. the first mixed solution prepared in the step a is stirred continuously at 40-60 DEG C, gradual solvent evaporated,
Solid will be obtained under air atmosphere, heat at least 2h at a temperature of not higher than 400 DEG C, obtain the first solid material；
C. using the mixed solution of second alcohol and water as solvent, by the first solid material obtained by the step b be dissolved in ethyl alcohol and
In the mixed solution of water, then weighs a certain amount of hydration 1.10- ferrosins and be also added in the mixed solution of second alcohol and water
The mass ratio of the addition of dissolving, the first solid material and a hydration 1.10- ferrosins is 1：(0.2~1.2), then in 40-60
It is stirred continuously mixed solution at DEG C, until gradually solvent evaporated, obtains the second solid material；
D. the second solid material of the gained in the step c is warming up to 800 DEG C to be not less than the heating rate of 5 DEG C/min
Calcination temperature then under 800 DEG C of calcination temperature, and roasts at least 2h in a nitrogen atmosphere, and it is negative to prepare mesoporous carbon-silica
Carry nanometer MoO3With the composite material of nano-metal particle.
2. the silica supported nanometer MoO of mesoporous carbon-according to claim 13With the preparation of the composite material of nano-metal particle
Method, it is characterised in that：In the step a, soluble inorganic metal salt uses any one in nickel salt, cobalt salt and molysite
Salt or arbitrary several salt-mixture.
3. the silica supported nanometer MoO of mesoporous carbon-according to claim 13With the preparation of the composite material of nano-metal particle
Method, it is characterised in that：In the step a, soluble inorganic metal salt uses nitrate.
4. the silica supported nanometer MoO of mesoporous carbon-according to claim 1 or claim 23With the composite material of nano-metal particle
Preparation method, it is characterised in that：In the step a, soluble inorganic metal salt is using Nickelous nitrate hexahydrate, six nitric hydrates
Cobalt and any one salt in six nitric hydrate iron or arbitrary several salt-mixture.
5. according to the silica supported nanometer MoO of any one of claims 1 to 3 mesoporous carbon-3With nano-metal particle
The preparation method of composite material, it is characterised in that：In the step a and c, when the mixed solution of second alcohol and water is as solvent,
The mixed volume ratio (v/v) of second alcohol and water is 1：(1~3).
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