CN109174155B - Preparation method and application of loose and porous silicon dioxide coated Co-N-C hollow nanotube material - Google Patents
Preparation method and application of loose and porous silicon dioxide coated Co-N-C hollow nanotube material 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 60
- 239000002071 nanotube Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 17
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 15
- 239000002073 nanorod Substances 0.000 claims abstract description 31
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 25
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 25
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 25
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 22
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SIURBWXPWMTEGD-UHFFFAOYSA-N CO.[Si](OCC)(O)(O)O Chemical compound CO.[Si](OCC)(O)(O)O SIURBWXPWMTEGD-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005406 washing 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 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 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
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000007062 hydrolysis Effects 0.000 abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 11
- 238000001354 calcination Methods 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical class [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
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- 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 preparation method and application of a loose and porous silicon dioxide coated Co-N-C hollow nanotube material, and MoO is prepared firstly3As nanorods, then on MoO3The surface of the nano rod is loaded with ZIF-67 to prepare MoO3@ ZIF-67 nanorod; then using MoO3As a self-sacrificing template, an aqueous solution of 2-methylimidazole can simultaneously provide dissolved MoO3And promoting SiO2Alkaline environment required by precursor hydrolysis is simply obtained to obtain orderly arranged ZIF-67@ SiO2Hollow nanorods; calcining at high temperature under the protection of nitrogen to obtain loose and porous hollow Co-N-C @ SiO2A nanotube. The catalyst can be used as a non-noble metal catalyst for efficiently catalyzing ammonia borane hydrolysis to produce hydrogen, and the TOF value can reach 8.4mol min under 298K‑ 1mol‑1 (Co)Has lower activation energy of 36.1kJ mol‑1And can achieve the reutilization property more than ten times.
Description
Technical Field
The invention belongs to the technical field of nano catalytic materials, and particularly relates to a preparation method and application of a loose and porous silicon dioxide coated Co-N-C hollow nanotube material.
Background
Hydrogen energy is increasingly gaining attention as the cleanest energy source, and boron-nitrogen compounds in hydrogen storage materials are particularly concerned due to the characteristics of high mass hydrogen storage density and easy dehydrogenation. Wherein, the ammonia borane has the mass hydrogen storage density of 19.6 percent, is stable at room temperature, and can be quickly hydrolyzed to release hydrogen under the action of a catalyst. The catalyst for catalyzing ammonia borane hydrolysis is mainly divided into a noble metal catalyst and a non-noble metal catalyst, the noble metal catalyst mainly comprises Rh, Ir, Ru, Pt and alloys thereof, and is the most efficient ammonia borane hydrolysis catalyst at present, but the wide application of the noble metal is limited due to scarcity and high price of the noble metal on the earth. Doping of noble metals with non-noble metals is a good option for cost reduction, but typically the noble metal content is over 75% to maintain its high catalytic and recycling properties.
At present, it is also an effective feasible scheme to design and synthesize catalysts for catalyzing ammonia borane hydrolysis by directly utilizing non-noble metals with high contents on earth, such as Fe, Co, Ni and Cu, and the catalysts mainly comprise Fe, Co, Ni and Cu nanoparticles and phosphide or oxide thereof. Among them, the Co nanoparticles exhibit excellent catalytic activity and tolerance, and their catalytic performance can be optimized by combining with a suitable carrier.
Disclosure of Invention
The invention aims to provide a preparation method and application of a loose and porous silicon dioxide coated Co-N-C hollow nanotube material. The composite nano material with excellent performance of catalyzing ammonia borane hydrolysis to generate hydrogen can be prepared by the method, and meanwhile, the preparation method is simple to operate, low in cost, mild in condition and environment-friendly.
The technical scheme adopted by the invention is as follows:
a preparation method of a loose and porous silicon dioxide coated Co-N-C hollow nanotube material comprises the following steps:
(1) preparation of MoO3A nanorod;
(2) methanol as solvent, MoO3Preparing MoO by using nano-rods, 2-methylimidazole and cobalt nitrate as raw materials3@ ZIF-67 nanorod;
(3) with MoO3@ ZIF-67 nanorod, 2-methylimidazole water solution and ethyl orthosilicate methanol solution are used as raw materials to prepare ZIF-67@ SiO2A nanotube;
(4) ZIF-67@ SiO2The nano tube is carbonized under the protection of nitrogen to prepare Co-N-C @ SiO2A nanotube.
The step (2) specifically comprises the following steps: dissolving 2-methylimidazole in methanol, and adding MoO when the 2-methylimidazole is completely dissolved3Adding a cobalt nitrate methanol solution after the nano rods are uniformly dispersed by ultrasonic, standing at room temperature for 2.5-3.5 h for reaction, centrifuging, and washing with methanol to obtain MoO3@ ZIF-67 nanorod.
In the step (2), the MoO3The ratio of the nano-rods to the 2-methylimidazole to the cobalt nitrate is (0.4-0.7) g: (4.0-5.0) g: (3.8-4.2) g; the concentration of the cobalt nitrate solution is 0.027-0.030 g/mL; the concentration of the 2-methylimidazole in methanolThe amount of the active carbon is 0.014-0.018 g/mL.
The step (3) specifically comprises the following steps: MoO obtained in the step (2)3@ ZIF-67 nano rod is dispersed in deionized water, 2-methylimidazole water solution is added under stirring, then ethyl orthosilicate methanol solution is added, stirring is carried out for 1 hour at room temperature, suction filtration, ethanol washing and drying are carried out, thus obtaining the ZIF-67@ SiO2A nanotube. The 2-methylimidazole aqueous solution in the raw material can be used for dissolving MoO at the same time3And promoting SiO2The precursor is hydrolyzed in an alkaline environment, ZIF-67 in the water environment can be stabilized, and the ZIF-67@ SiO is quickly generated2A nanotube.
In the step (3), the MoO3The volume ratio of the @ ZIF-67 aqueous solution, the 2-methylimidazole aqueous solution and the ethyl orthosilicate methanol solution is 1: 0.8-1.2: 0.1 to 0.5; the concentration of the 2-methylimidazole water solution is 0.08-0.125 g/mL; the volume ratio of the ethyl orthosilicate to the methanol in the methanol solution of the ethyl orthosilicate is 1: 7-9.
In the step (4), carbonizing at 650-850 ℃ for 2h in a tube furnace; the temperature rise rate of the tubular furnace is 0.5-1.5 ℃ min-1(ii) a Preferably carbonized at 800 ℃ for 2 h.
The invention also provides the loose and porous silicon dioxide coated Co-N-C hollow nanotube material prepared by the preparation method. The loose and porous silicon dioxide coated Co-N-C hollow nanotube material is MoO3The nanorod is a self-sacrifice template to obtain uniformly coated ZIF-67@ SiO2Nanotube, high-temperature calcining under nitrogen protection to form SiO2The coated nitrogen-doped carbon hollow nanotube carrier is uniformly loaded with small-size Co nanoparticles, and the diameter of the structure is 500-600 nm.
The invention also provides application of the loose and porous silicon dioxide coated Co-N-C hollow nanotube material in catalytic hydrogen production. The loose and porous Co-N-C hollow nanotube material coated with the silicon dioxide can catalyze ammonia borane to generate hydrogen, and the TOF value can reach 8.4mol min under 298K-1mol-1 (Co)Activation energy as low as 36.1kJ mol-1。
The invention firstly prepares MoO3Nanorods followed by a MoO3Coating ZIF-67 on the surface of the nano-rod to obtain MoO3@ ZIF-67 nanorod; then using MoO3As a self-sacrificing template, an aqueous solution of 2-methylimidazole can simultaneously provide dissolved MoO3And promoting SiO2Alkaline environment required by precursor hydrolysis is simply obtained to obtain orderly arranged ZIF-67@ SiO2Hollow nanorods; and calcining at high temperature under the protection of nitrogen to obtain the loose and porous Co-N-C hollow nanotube material coated with silicon dioxide. The loose and porous hollow rod-shaped structure is beneficial to the transmission of molecules in solution, and SiO is generated in the calcining process2The coated nitrogen-doped carbon support provides sufficient room for the Co nanoparticles to effectively control the size and dispersion of the particles.
Compared with the prior art, the loose and porous silicon dioxide coated Co-N-C hollow nanotube material disclosed by the invention has the advantages of simple preparation process, mild condition, low cost and novel method, no stabilizer or surfactant is required to be added in the reaction process, the synthesis process and the post-treatment of the product are convenient, the size and the morphology of the material are easy to regulate and control, and the loose and porous silicon dioxide coated Co-N-C hollow nanotube material is suitable for large-scale production. Can be used as a non-noble metal catalyst for efficiently catalyzing ammonia borane hydrolysis to produce hydrogen. TOF value can reach 8.4mol min under 298K-1mol-1 (Co)Has lower activation energy of 36.1kJ mol-1And can achieve the reutilization property more than ten times.
Drawings
FIG. 1 is a schematic diagram of the mechanism of a loose porous silica coated Co-N-C hollow nanotube material;
FIG. 2 is MoO in example 13Sem (a) and TEM images (b);
FIG. 3 is SEM (a) and TEM image (b) of A1 in example 1;
FIG. 4 is an XRD (a), SEM (b), TEM (c) and Mapping plot (d) of A2 in example 1;
FIG. 5 is SEM (a), TEM (b), mapping (c), BET (d) and XPS plots (e, f, g, h) of A3 obtained by carbonization at 800 ℃ in example 1;
fig. 6 is an SEM image of A3 obtained by carbonization at 650 ℃ (a), 750 ℃ (b), 850 ℃ (c) and a TEM image of A3 obtained by carbonization at 650 ℃ (d), 750 ℃ (e), 850 ℃ (f), respectively, in example 1;
FIG. 7 is a comparative graph of XRD of A3 obtained by carbonizing example 1 at 650 deg.C, 750 deg.C, 800 deg.C, 850 deg.C;
FIG. 8 is a graph showing the results of the catalytic hydrogen production performance of the loose and porous silica-coated Co-N-C hollow nanotube material of example 2, wherein (a) is the performance of the loose and porous silica-coated Co-N-C hollow nanotube material obtained by carbonization at different temperatures in catalyzing ammonia borane hydrolysis to produce hydrogen; (b) 800 ℃ Co-N-C @ SiO for optimum performance under different calcination temperature contrast2The catalytic hydrogen production performance diagram of ammonia borane aqueous solution under different test temperatures; (c) fitting the performance data at each test temperature in the graph (b) to obtain a graph of activation energy; (d) as a result of comparison with catalytic hydrogen production performance of other catalysts; FIG. e shows 800 ℃ Co-N-C @ SiO2The material was tested ten times for a performance cycle chart.
FIG. 9 shows the Co-N-C @ SiO obtained in example 2 after calcination and carbonization at 800 deg.C2Xrd (a) and SEM images (b) before and after durability cycle testing of the tubular nanomaterial.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
A preparation method of a loose and porous silicon dioxide coated Co-N-C hollow nanotube material comprises the following steps:
(1) preparation of MoO3Nanorod (a 1): 6.665mL of nitric acid is taken by a 1000mL liquid transfer gun to be mixed with 33.335mL of deionized water, 1.4g of ammonium molybdate is weighed, added into the supernatant, stirred for 20min, transferred to a 100mL reaction kettle, reacted in an oven at 200 ℃ for 20h, cooled and centrifugally washed to obtain MoO3The SEM and TEM images of the dried product are shown in FIG. 2(a) and FIG. 2(b), respectively, and it can be seen from the images that the MoO is obtained3Is a solid nano rod-shaped structure with the diameter of 300 nm;
(2) preparation of MoO3@ ZIF-67 nanorod (A2): 4.5982g of 2-methylimidazole are weighed out and dissolved in 280mL of methanol, and added until the solution is completely dissolved0.5g MoO3Adding 140mL of Co (NO) with 0.03g/mL after uniform ultrasonic dispersion3)2Standing the methanol solution at room temperature for 3h, and centrifuging and washing the methanol solution to obtain MoO3@ ZIF-67 nanorod; SEM and TEM images of the resulting MoO are shown in FIG. 3(a) and FIG. 3(b), respectively, and it can be seen from these images3@ ZIF-67 nano rod is in MoO3The surface of the nanorod is coated with a layer of ZIF-67 with the thickness of 150-200 nm to form a rod-shaped structure with the diameter of about 600 nm;
(3) preparation of ZIF-67@ SiO2Nanotube (a 3): adding MoO3@ ZIF-67 nanorods dispersed in 280mL of deionized water, 280mL of a 0.1g/mL aqueous solution of 2-methylimidazole was added under vigorous stirring, followed by 90mL of a methanol solution of Tetraethylorthosilicate (TEOS) having a volume ratio of TEOS to methanol of 1: 8, stirring for 1 hour at room temperature, filtering, collecting a product, washing with ethanol for three times, and drying at 60 ℃ to obtain ZIF-67@ SiO2A nanotube; the detection results of the product A3 by X-ray diffraction (XRD), SEM, TEM and Mapping are respectively shown in FIG. 4(a), FIG. 4(b), FIG. 4(c) and FIG. 4(d), the TEM image shows that the product A3 is a hollow nano-tube structure with the diameter of 600nm, and the XRD and Mapping images further show that no MoO exists in the product3To obtain ZIF-67@ SiO2A nanotube;
(4) preparation of Co-N-C @ SiO2Nanotube (a 4): 3.0g of ZIF-67@ SiO2The nanotubes were placed in a tube furnace and heated at N2Carbonizing at target temperature of 650 deg.C, 750 deg.C, 800 deg.C, and 850 deg.C for 2 hr under atmosphere, and setting heating rate to 1 deg.C for min-1To prepare Co-N-C @ SiO2A nanotube;
the samples obtained by carbonization at 800 ℃ were examined by SEM, TEM, Mapping, nitrogen adsorption-desorption (BET), and X-ray fine diffraction (XPS), as shown in fig. 5(a), 5(b), 5(c), 5(d), and 5(e to h), respectively; SEM of the samples obtained by carbonizing at 650 deg.C, 750 deg.C and 850 deg.C are shown in FIG. 6(a), FIG. 6(b) and FIG. 6(c), and TEM of the samples obtained by carbonizing at 650 deg.C, 750 deg.C and 850 deg.C are shown in FIG. 6(d), FIG. 6(e) and FIG. 6(f), respectively.As can be seen from FIGS. 5 (a-C) and 6, the product is a hollow nanotube-like structure, and the Co nanoparticles are uniformly distributed on the small lattices of the tube wall, and as can be seen from FIGS. 5 (e-h), the target product obtained in this example is a loose and porous silica-coated Co-N-C hollow nanotube material (Co-N-C @ SiO)2)。
And XRD was used to detect A4, as shown in FIG. 7, which is consistent with standard card PDF-15-0806 from Co. The detection result further indicates that the obtained product is a loose and porous silicon dioxide coated Co-N-C hollow nanotube material.
Example 2
Application of loose and porous silicon dioxide coated Co-N-C hollow nanotube material in catalyzing ammonia borane to generate hydrogen
Firstly 10mg of Co-N-C @ SiO2The catalyst was pretreated with freshly prepared 10mL of 3.3mg/mL Ammonia Borane (AB) in water in a 25mL two-necked round bottom flask for 12min to improve Co-N-C @ SiO2Dispersion of (2). One port was then sealed with a rubber cap and the other port was connected with a gas collection system. Then, 0.5mL of an aqueous AB solution having a concentration of 66mg/mL was rapidly injected into the reaction system with vigorous stirring at 1000 rpm. The gas produced by hydrolysis was measured by a typical water displacement method. The durability cycling test was performed by adding another equal amount of 0.5mL of 66mg/mL aqueous AB solution to the reaction system after the added AB solution had reacted to completion, and collecting the released hydrogen again and measuring.
The gas collecting device is used for measuring the hydrogen production performance of the catalyst in catalyzing ammonia borane hydrolysis, as shown in fig. 8, the material performance after calcination and carbonization at 800 ℃ is the best. TOF value can reach 8.4mol min under 298K-1mol-1 (Co)Has lower activation energy of 36.1kJ mol-1And can achieve the reutilization property more than ten times.
FIG. 9 shows the Co-N-C @ SiO obtained after calcination and carbonization at 800 DEG C2XRD (a) and SEM (b) of the hollow nanotube material after durability cycle test, and Co-N-C @ SiO can be seen from the figure2After the material is recycled, the appearance and the crystal phase of the material are approximately unchanged, and the material has better cyclic catalytic performance.
The above detailed description of the method of making a loose porous silica coated Co-N-C hollow nanotube material and its applications with reference to the examples is illustrative and not restrictive, and several examples can be cited within the limits set forth, so that variations and modifications that do not depart from the general concept of the present invention are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a loose and porous silicon dioxide coated Co-N-C hollow nanotube material is characterized by comprising the following steps:
(1) preparation of MoO3A nanorod;
(2) methanol as solvent, MoO3Preparing MoO by using nano-rods, 2-methylimidazole and cobalt nitrate as raw materials3@ ZIF-67 nanorod;
(3) with MoO3@ ZIF-67 nanorod, 2-methylimidazole water solution and ethyl orthosilicate methanol solution are used as raw materials to prepare ZIF-67@ SiO2A nanotube;
(4) ZIF-67@ SiO2The nano tube is carbonized under the protection of nitrogen to prepare Co-N-C @ SiO2A nanotube.
2. The preparation method according to claim 1, wherein the step (2) specifically comprises the steps of: dissolving 2-methylimidazole in methanol, and adding MoO when the 2-methylimidazole is completely dissolved3Adding a cobalt nitrate methanol solution after the nano rods are uniformly dispersed by ultrasonic, standing at room temperature for 2.5-3.5 h for reaction, centrifuging, and washing with methanol to obtain MoO3@ ZIF-67 nanorod.
3. The method according to claim 1 or 2, wherein in the step (2), the MoO is3The ratio of the nano-rods to the 2-methylimidazole to the cobalt nitrate is (0.4-0.7) g: (4.0-5.0) g: (3.8-4.2) g.
4. The method according to claim 1, wherein the step (a), (b), (c) and (d)3) The method specifically comprises the following steps: MoO obtained in the step (2)3@ ZIF-67 nano rod is dispersed in deionized water to obtain MoO3@ ZIF-67 aqueous solution, adding 2-methylimidazole aqueous solution under stirring, then adding ethyl orthosilicate methanol solution, stirring for 1 hour at room temperature, filtering, washing with ethanol, and drying to obtain the ZIF-67@ SiO2A nanotube.
5. The method according to claim 4, wherein in the step (3), the MoO is3The volume ratio of the @ ZIF-67 aqueous solution, the 2-methylimidazole aqueous solution and the ethyl orthosilicate methanol solution is 1: 0.8-1.2: 0.1 to 0.5; the concentration of the 2-methylimidazole water solution is 0.08-0.125 g/mL; the volume ratio of the ethyl orthosilicate to the methanol in the methanol solution of the ethyl orthosilicate is 1: 7-9.
6. The preparation method according to claim 1, wherein in the step (4), the carbonization is performed in a tube furnace at 650-850 ℃ for 2 h; the temperature rise rate of the tubular furnace is 0.5-1.5 ℃/min.
7. The method according to claim 6, wherein in the step (4), the carbonization is performed in a tube furnace at 800 ℃ for 2 hours.
8. The loose and porous silica-coated Co-N-C hollow nanotube material prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the loose porous silica-coated Co-N-C hollow nanotube material of claim 8 in the catalytic hydrogen production.
10. The use of claim 9, wherein the loose porous silica-coated Co-N-C hollow nanotube material catalyzes ammonia borane to generate hydrogen gas, and the activation energy is as low as 36.1 kJ/mol at 298K.
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| CN112978870B (en) * | 2021-03-25 | 2022-06-14 | 辽宁大学 | MoO3-xPreparation method and application of/C/CoO nano composite material |
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