CN109174155A - A kind of preparation method and applications of loose porous coated with silica Co-N-C hollow Nano tube material - Google Patents
A kind of preparation method and applications of loose porous coated with silica Co-N-C hollow Nano tube material Download PDFInfo
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- CN109174155A CN109174155A CN201811094363.0A CN201811094363A CN109174155A CN 109174155 A CN109174155 A CN 109174155A CN 201811094363 A CN201811094363 A CN 201811094363A CN 109174155 A CN109174155 A CN 109174155A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002071 nanotube Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 33
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229910000085 borane Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- SIURBWXPWMTEGD-UHFFFAOYSA-N CO.[Si](OCC)(O)(O)O Chemical compound CO.[Si](OCC)(O)(O)O SIURBWXPWMTEGD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000007062 hydrolysis Effects 0.000 abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000002073 nanorod Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GQWNECFJGBQMBO-UHFFFAOYSA-N Molindone hydrochloride Chemical compound Cl.O=C1C=2C(CC)=C(C)NC=2CCC1CN1CCOCC1 GQWNECFJGBQMBO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of preparation method and applications of loose porous coated with silica Co-N-C hollow Nano tube material, are prepared for MoO first3Make nanometer rods, then in MoO3Make ZIF-67 on the area load of nanometer rods, MoO is prepared3@ZIF-67 nanometer rods；Then MoO is utilized3As from template is sacrificed, 2-methylimidazole aqueous solution can provide dissolution MoO simultaneously3With promote SiO2The alkaline environment that presoma hydrolysis needs, is simply obtained the ZIF-67@SiO of ordered arrangement2Hollow nanorod；High-temperature calcination obtains loose porous hollow Co-N-C@SiO under nitrogen protection again2Nanotube.It can be used as the non-precious metal catalyst that efficient catalytic ammonia borane hydrolysis produces hydrogen, and TOF value can reach 8.4mol min at 298K‑1mol‑1 (Co), there is lower activation energy 36.1kJ mol‑1, and reusing more than ten times can be reached.
Description
Technical field
The invention belongs to nano catalytic material technical fields, and in particular to a kind of loose porous coated with silica Co-
The preparation method and applications of N-C hollow Nano tube material.
Background technique
Hydrogen Energy is increasingly valued by people as a kind of most clean energy, in hydrogen storage material, boron-nitrogen compound by
In the high quality hydrogen-storage density and easy dehydrogenation the characteristics of and paid special attention to.Wherein, ammonia borine has 19.6% quality
Hydrogen-storage density, and it is very stable at room temperature, playing the role of catalyst can fast hydrolyzing release hydrogen.It is catalyzed ammonia borane hydrolysis
Catalyst is broadly divided into noble metal catalyst and non-precious metal catalyst, and noble metal catalyst mainly has a Rh, Ir, Ru, Pt and it
Alloy, be current most efficient ammonia borane hydrolysis catalyst, but the rare and expensive limit due to noble metal on earth
Their extensive use is made.In order to reduce cost, it is a kind of selection well that base metal is adulterated in noble metal, but general
Bullion content will be more than 75% to keep its high catalytic property and reusing.
Currently, directly utilize Fe, Co, Ni, the more base metal of content designs synthesis catalytic ammonia on these earth of Cu
The catalyst of borane hydrolysis is also a kind of effective feasible scheme, these catalyst are mainly Fe, Co, Ni, Cu nano particle
With their phosphide or oxide.Wherein, Co nano particle shows excellent catalytic activity and tolerance, can pass through knot
It closes suitable carrier and then optimizes its catalytic performance.
Summary of the invention
The purpose of the present invention is to provide a kind of loose porous coated with silica Co-N-C hollow Nano tube materials
Preparation method and applications.The composite Nano material with excellent catalysis ammonia borane hydrolysis H2-producing capacity can be made by this method
Material, while the preparation method is easy to operate, low in cost, mild condition, environmentally protective.
The technical scheme adopted by the invention is as follows:
A kind of preparation method of loose porous coated with silica Co-N-C hollow Nano tube material, including following step
It is rapid:
(1) MoO is prepared3Nanometer rods；
(2) using methanol as solvent, MoO3Nanometer rods, 2-methylimidazole, cobalt nitrate are raw material, prepare MoO3ZIF-67 nanometers of@
Stick；
(3) with MoO3@ZIF-67 nanometer rods, 2-methylimidazole aqueous solution, ethyl orthosilicate methanol solution be raw material, system
Standby ZIF-67@SiO2Nanotube；
(4) by ZIF-67@SiO2Co-N-C@SiO is prepared in nanotube after being carbonized under the protection of nitrogen2Nanotube.
The step (2) is to be dissolved to be added completely into MoO specifically includes the following steps: 2-methylimidazole is dissolved in methanol3
Cobalt nitrate methanol solution is added after nanometer rods ultrasonic disperse is uniform, is stored at room temperature 2.5~3.5h of reaction, is centrifuged, is washed through methanol
MoO is obtained after washing3@ZIF-67 nanometer rods.
In the step (2), the MoO3Nanometer rods, 2-methylimidazole, cobalt nitrate ratio be (0.4~0.7) g:
(4.0~5.0) g:(3.8-4.2) g；The concentration of the cobalt nitrate solution is 0.027~0.030g/mL；The 2-methylimidazole
Concentration in methyl alcohol is 0.014~0.018g/mL.
The step (3) is specifically includes the following steps: the MoO that step (2) is obtained3@ZIF-67 nanometer rods are distributed to
In ionized water, 2-methylimidazole aqueous solution is added under stiring, the methanol solution of ethyl orthosilicate is then added, stirs at room temperature
It 1 hour, filters, through ethanol washing, drying, the ZIF-67@SiO can be obtained2Nanotube.2-methylimidazole water in raw material
Solution can be simultaneously as dissolution MoO3With promote SiO2The alkaline environment that presoma hydrolysis needs, and can stablize in water environment
ZIF-67, quickly generate ZIF-67@SiO2Nanotube.
In step (3), the MoO3@ZIF-67 aqueous solution, 2-methylimidazole aqueous solution, ethyl orthosilicate methanol solution
The ratio between volume be 1:0.8~1.2:0.1~0.5；The concentration of the 2-methylimidazole aqueous solution is 0.08~0.125g/mL；
The ratio between volume of ethyl orthosilicate and methanol is 1:7~9 in the methanol solution of the ethyl orthosilicate.
In step (4), the carbonization is referred in tube furnace in 650~850 DEG C of carbonization 2h；The heating rate of tube furnace
For 0.5~1.5 DEG C of min-1；Preferably in 800 DEG C of carbonization 2h.
The loose porous coated with silica Co-N-C being prepared the present invention also provides the preparation method is empty
Heart nano-tube material.The loose porous coated with silica Co-N-C hollow Nano tube material is with MoO3Nanometer rods are certainly
Sacrifice the ZIF-67 SiO that template is uniformly coated2Nanotube, high-temperature calcination forms SiO under nitrogen protection2The nitrogen of cladding
This structure of uniform load small size Co nano particle on the carbon hollow nanotube carrier of doping, diameter is in 500~600nm.
The present invention also provides the loose porous coated with silica Co-N-C hollow Nano tube materials to be catalyzed
Produce the application in hydrogen.The loose porous coated with silica Co-N-C hollow Nano tube material can be catalyzed ammonia borine and generate hydrogen
Gas, TOF value can reach 8.4mol min at 298K-1mol-1 (Co), activation energy is down to 36.1kJ mol-1。
The method comprises the steps of firstly, preparing MoO3Nanometer rods, then in MoO3ZIF-67 is wrapped on the surface of nanometer rods, is prepared
MoO3@ZIF-67 nanometer rods；Then MoO is utilized3As from template is sacrificed, 2-methylimidazole aqueous solution can provide dissolution simultaneously
MoO3With promote SiO2The alkaline environment that presoma hydrolysis needs, is simply obtained the ZIF-67@SiO of ordered arrangement2Hollow Nano
Stick；High-temperature calcination obtains loose porous coated with silica Co-N-C hollow Nano tube material under nitrogen protection again.Its
Loose porous hollow club shaped structure is conducive to the transmission of molecules in solution, and the SiO in calcination process2The carbon of the N doping of cladding
Carrier provides enough spaces to Co nano particle and efficiently controls the size and dispersibility of particle.
Compared with prior art, the loose porous coated with silica Co-N-C hollow Nano tubing of disclosure of the invention
The preparation process of material is simple, mild condition, low in cost, method is novel, during the reaction without be added any stabilizer or
Surfactant, the synthesis process and convenient post-treatment of product are easy to regulate and control the size and shape of material, are suitble to big rule
Mould production.It can be used as the non-precious metal catalyst that efficient catalytic ammonia borane hydrolysis produces hydrogen.TOF value can reach 8.4mol at 298K
min-1mol-1 (Co), there is lower activation energy 36.1kJ mol-1, and reusing more than ten times can be reached.
Detailed description of the invention
Fig. 1 is the mechanism figure of loose porous coated with silica Co-N-C hollow Nano tube material；
Fig. 2 is MoO in embodiment 13SEM (a) and TEM figure (b)；
Fig. 3 is SEM (a) and the TEM figure (b) of A1 in embodiment 1；
Fig. 4 is the XRD (a) of A2 in embodiment 1, SEM (b), TEM (c) and Mapping figure (d)；
Fig. 5 be carbonized at 800 DEG C in embodiment 1 acquisition A3 SEM (a), TEM (b), Mapping (c), BET (a)
(e, f, g, h) is schemed with XPS；
Fig. 6 be in embodiment 1 respectively 650 DEG C (a), 750 DEG C (b), 850 DEG C (c) carbonization obtain A3 SEM figure and
In the TEM figure for the A3 that 650 DEG C (d), 750 DEG C (e), 850 DEG C (f) carbonizations obtain；
The embodiment 1 of Fig. 7 be carbonized at 650 DEG C, 750 DEG C, 800 DEG C, 850 DEG C acquisition A3 XRD comparison diagram；
Fig. 8 is that the catalysis of coated with silica Co-N-C hollow Nano tube material loose porous in embodiment 2 produces hydrogen
Energy test result, wherein (a) is the loose porous coated with silica Co-N-C hollow Nano being carbonized under different temperatures
Tube material is catalyzed ammonia borane hydrolysis H2-producing capacity figure；(b) 800 DEG C of Co-N- of lower best performance is compared for different calcination temperatures
C@SiO2To the catalysis H2-producing capacity figure of ammonia borine aqueous solution under different test temperatures；(c) it serves as reasons each test temperature in (b) figure
The figure of activation energy is sought in lower performance data fitting；It (d) is the comparison result of the catalysis H2-producing capacity with other catalyst；Scheming (e) is
800 DEG C of Co-N-C@SiO2Ten performance cycle figures of testing of materials.
Fig. 9 is the Co-N-C@SiO obtained after 800 DEG C of calcining carbonizations in embodiment 22Tubular nanometer material is followed through durability
XRD (a) and SEM figure (b) before and after ring test.
Specific embodiment
Below with reference to embodiment and Figure of description, the present invention is described in detail.
Embodiment 1
A kind of preparation method of loose porous coated with silica Co-N-C hollow Nano tube material, including following step
It is rapid:
(1) MoO is prepared3Nanometer rods (A1): with the liquid-transfering gun of 1000mL take 6.665mL nitric acid and 33.335mL go from
Sub- water mixing, then weigh after upper liquid stirring 20min is added in 1.4g ammonium molybdate and be transferred to 100mL reaction kettle, 200 DEG C of baking oven reactions
20h, centrifuge washing obtains MoO after cooling3Such as Fig. 2 (a), Fig. 2 (b) are shown respectively for drying, SEM and TEM figure, can from figure
To find out, obtained MoO3For diameter 300nm solid nano bar-shape structure；
(2) MoO is prepared3@ZIF-67 nanometer rods (A2): weighing 4.5982g 2-methylimidazole and be dissolved in 280mL methanol, to
Dissolution is added completely into 0.5g MoO3Co (the NO of 140mL 0.03g/mL is added after ultrasonic disperse is uniform3)2Methanol solution, room temperature
3h is stood, centrifugation methanol washing obtains MoO3@ZIF-67 nanometer rods；Its SEM and TEM figure is respectively such as Fig. 3 (a), Fig. 3 (b) institute
Show, it can be seen from the figure that MoO obtained3@ZIF-67 nanometer rods are in MoO3The surface of nanometer rods has coated a layer thickness
Club shaped structure of the diameter that the ZIF-67 of 150~200nm is formed in 600nm or so；
(3) ZIF-67@SiO is prepared2Nanotube (A3): by MoO3@ZIF-67 nanometer rods are distributed in 280mL deionized water,
The aqueous solution of 280mL 0.1g/mL 2-methylimidazole is added with vigorous stirring, 90mL tetraethyl orthosilicate is then added
(TEOS) methanol solution, the ratio between volume of TEOS and methanol is 1:8 in the methanol solution of the tetraethyl orthosilicate (TEOS),
Collected by suction product after stirring 1 hour at room temperature, it is three times and dry at 60 DEG C with ethanol washing, ZIF-67@is prepared
SiO2Nanotube；Product A3 is detected with X-ray diffraction (XRD), SEM, TEM and mapping, as a result respectively such as Fig. 4
(a), shown in Fig. 4 (b), Fig. 4 (c), Fig. 4 (d), from TEM figure as can be seen that product A3 is hollow nanotube of the diameter in 600nm
Shape structure, XRD and Mapping figure further illustrate in product without MoO3, that obtain is ZIF-67@SiO2Nanotube；
(4) Co-N-C@SiO is prepared2Nanotube (A4): by 3.0g ZIF-67@SiO2Nanotube be placed in tube furnace and
N2It is carbonized 2 hours at 650 DEG C, 750 DEG C, 800 DEG C, 850 DEG C of target temperature respectively under atmosphere, adding when being warming up to target temperature
Hot rate is set as 1 DEG C of min-1, Co-N-C@SiO is prepared2Nanotube；
With SEM, TEM, Mapping, nitrogen adsorption desorption instrument (BET) and the fine diffraction of X-ray (XPS) in 800 DEG C of carbon
Change sample obtained to be detected, respectively as shown in Fig. 5 (a), Fig. 5 (b), Fig. 5 (c), Fig. 5 (d), Fig. 5 (e~h)；650℃,
The SEM of 750 DEG C, 850 DEG C carbonization samples obtained respectively as shown in Fig. 6 (a), Fig. 6 (b), Fig. 6 (c), 650 DEG C, 750 DEG C,
The TEM of 850 DEG C of carbonization samples obtained is respectively as shown in Fig. 6 (d), Fig. 6 (e), Fig. 6 (f).It can be with from Fig. 5 (a~c) and Fig. 6
Find out, product is hollow Nano tubulose structure, and Co nano particle is evenly distributed on everywhere in tube wall sub-box, from Fig. 5 (e~
H) as can be seen that the purpose product that the present embodiment obtains is loose porous coated with silica Co-N-C hollow Nano tube material
(Co-N-C@SiO2)。
And A4 is detected with XRD, as shown in fig. 7, its result is consistent with the standard card PDF-15-0806 of Co.Testing result
Obtained product is a kind of loose porous coated with silica Co-N-C hollow Nano tube material.
Embodiment 2
Loose porous coated with silica Co-N-C hollow Nano tube material generates answering in hydrogen in catalysis ammonia borine
With
First by 10mg Co-N-C@SiO2The ammonia borine (AB) that catalyst is 3.3mg/mL with freshly prepd 10mL concentration
Aqueous solution pre-processes 12min in the neck round bottom flask of 25mL, to improve Co-N-C@SiO2Dispersibility.Then rubber is used
Lid one mouth of sealing, another mouth are connected with gas gathering system.Then it is vigorously stirred in 1000rpm and lower is by 0.5mL concentration
The AB aqueous solution of 66mg/mL is rapidly injected in reaction system.The gas generated by the measurement of typical water displacement method by hydrolysis.It is resistance to
Long property loop test is that the AB that the 0.5mL concentration of another equivalent is 66mg/mL is added after the AB solution reaction being added is complete
Aqueous solution collects the hydrogen of release and measurement into reaction system again.
Catalyst ammonia borane hydrolysis H2-producing capacity is measured using gas collector, as shown in figure 8, can from figure
To find out that the material property through 800 DEG C of calcining carbonizations is best.TOF value can reach 8.4mol min at 298K-1mol-1 (Co), tool
There is lower activation energy 36.1kJ mol-1, and reusing more than ten times can be reached.
Fig. 9 is the Co-N-C@SiO obtained after 800 DEG C of calcinings are carbonized2Hollow Nano tube material is after durability loop test
XRD (a) and SEM figure (b), it can be seen from the figure that Co-N-C@SiO2Material is after being recycled, pattern and crystal phase
It is substantially constant, there is preferable circulation catalytic performance.
A kind of above-mentioned preparation referring to embodiment to loose porous coated with silica Co-N-C hollow Nano tube material
The detailed description that method and its application carry out, is illustrative without being restrictive, if can enumerate according to limited range
Dry embodiment, therefore the change and modification in the case where not departing from present general inventive concept, should belong within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of loose porous coated with silica Co-N-C hollow Nano tube material, which is characterized in that packet
Include following steps:
(1) MoO is prepared3Nanometer rods；
(2) using methanol as solvent, MoO3Nanometer rods, 2-methylimidazole, cobalt nitrate are raw material, prepare MoO3@ZIF-67 nanometer rods；
(3) with MoO3@ZIF-67 nanometer rods, 2-methylimidazole aqueous solution, ethyl orthosilicate methanol solution be raw material, preparation
ZIF-67@SiO2Nanotube；
(4) by ZIF-67@SiO2Co-N-C@SiO is prepared in nanotube after being carbonized under the protection of nitrogen2Nanotube.
2. preparation method according to claim 1, which is characterized in that the step (2) is specifically includes the following steps: by 2-
Methylimidazole is dissolved in methanol, to be dissolved to be added completely into MoO3It is molten that cobalt nitrate methanol is added after nanometer rods ultrasonic disperse is uniform
Liquid is stored at room temperature 2.5~3.5h of reaction, and centrifugation obtains MoO after methanol washs3@ZIF-67 nanometer rods.
3. preparation method according to claim 1 or 2, which is characterized in that in the step (2), the MoO3Nanometer rods,
2-methylimidazole, cobalt nitrate ratio be (0.4~0.7) g:(4.0~5.0) g:(3.8-4.2) g；The cobalt nitrate solution
Concentration is 0.027~0.030g/mL；The concentration of the 2-methylimidazole in methyl alcohol is 0.014~0.018g/mL.
4. preparation method according to claim 1, which is characterized in that the step (3) is specifically includes the following steps: will step
Suddenly the MoO that (2) obtain3@ZIF-67 nanometer rods are distributed in deionized water, 2-methylimidazole aqueous solution are added under stiring, so
The methanol solution of ethyl orthosilicate is added afterwards, stirs 1 hour at room temperature, filters, through ethanol washing, drying, can be obtained described
ZIF-67@SiO2Nanotube.
5. preparation method according to claim 1 or 4, which is characterized in that in step (3), the MoO3@ZIF-67 is water-soluble
The ratio between volume of methanol solution of liquid, 2-methylimidazole aqueous solution, ethyl orthosilicate is 1:0.8~1.2:0.1~0.5；It is described
The concentration of 2-methylimidazole aqueous solution is 0.08~0.125g/mL；Ethyl orthosilicate in the methanol solution of the ethyl orthosilicate
It is 1:7~9 with the ratio between the volume of methanol.
6. preparation method according to claim 1, which is characterized in that in step (4), the carbonization is referred in tube furnace
In in 650~850 DEG C of carbonization 2h；The heating rate of tube furnace is 0.5~1.5 DEG C of min-1。
7. preparation method according to claim 6, which is characterized in that in step (4), the carbonization is referred in tube furnace
In in 800 DEG C of carbonization 2h.
8. the loose porous coated with silica that preparation method described in -7 any one is prepared according to claim 1
Co-N-C hollow Nano tube material.
9. loose porous coated with silica Co-N-C hollow Nano tube material according to claim 8 produces hydrogen in catalysis
In application.
10. application according to claim 9, which is characterized in that the loose porous coated with silica Co-N-C is empty
Heart nano-tube material can be catalyzed ammonia borine and generate hydrogen, and TOF value can reach 8.4mol min at 298K-1mol-1 (Co), activation energy
Down to 36.1kJ mol-1。
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|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785273A (en) * | 2015-03-30 | 2015-07-22 | 福州大学 | Co-Mo system water gas shift catalyst and preparation method thereof |
| CN106564875A (en) * | 2016-11-09 | 2017-04-19 | 江苏理工学院 | Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles |
| CN106829924A (en) * | 2017-03-15 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of one-dimensional porous CNT |
| CN106902842A (en) * | 2017-03-20 | 2017-06-30 | 北京工业大学 | A kind of preparation and application for deriving load type palladium catalyst of the carbon-based material as carrier with MOFs |
-
2018
- 2018-09-19 CN CN201811094363.0A patent/CN109174155B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785273A (en) * | 2015-03-30 | 2015-07-22 | 福州大学 | Co-Mo system water gas shift catalyst and preparation method thereof |
| CN106564875A (en) * | 2016-11-09 | 2017-04-19 | 江苏理工学院 | Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles |
| CN106829924A (en) * | 2017-03-15 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of one-dimensional porous CNT |
| CN106902842A (en) * | 2017-03-20 | 2017-06-30 | 北京工业大学 | A kind of preparation and application for deriving load type palladium catalyst of the carbon-based material as carrier with MOFs |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109888310A (en) * | 2019-03-04 | 2019-06-14 | 上海交通大学 | Porous carbon coating non-noble metal alloy compound oxygen reduction catalyst of N doping and preparation method thereof |
| CN109950056A (en) * | 2019-04-09 | 2019-06-28 | 哈尔滨理工大学 | A kind of preparation of hollow NiO@N-C nanometer tube combination electrode material |
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| CN110299530A (en) * | 2019-07-22 | 2019-10-01 | 福州大学 | A kind of ZIF-67 base cobalt molybdenum oxide hollow Nano cage/graphene composite material and the preparation method and application thereof |
| CN110299530B (en) * | 2019-07-22 | 2022-04-01 | 福州大学 | ZIF-67-based cobalt molybdenum oxide hollow nanocage/graphene composite material and preparation method and application thereof |
| CN110591388A (en) * | 2019-08-22 | 2019-12-20 | 安徽建筑大学 | Flame-retardant smoke suppressant containing cobalt, nitrogen and silicon and preparation method thereof |
| CN111446440A (en) * | 2020-05-22 | 2020-07-24 | 扬州大学 | Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof |
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| CN112808235B (en) * | 2020-12-31 | 2021-11-23 | 华南理工大学 | Co @ NCNT material prepared by reduction-oxidation-reduction strategy and preparation method thereof |
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