CN105110315A - Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template - Google Patents
Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template Download PDFInfo
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- CN105110315A CN105110315A CN201510448674.2A CN201510448674A CN105110315A CN 105110315 A CN105110315 A CN 105110315A CN 201510448674 A CN201510448674 A CN 201510448674A CN 105110315 A CN105110315 A CN 105110315A
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Abstract
The invention discloses a method for synthesis of a double-casing layer carbon nanometer hollow polyhedron by a metal-organic framework as a template and belongs to the field of novel energy and novel materials. The method comprises that a zeolitic imidazolate framework with a core-shell nanometer structure as a structure precursor is calcined at a high temperature to form the double-casing layer nanometer carbon hollow polyhedron. The cheap and easily available zeolitic imidazolate framework as a structure precursor is used for preparation of the double-casing layer carbon nanometer hollow polyhedron. The method has simple processes, is free of a template, realizes precise control of a shell structure by change of a zinc/cobalt-based zeolitic imidazolate framework ratio or calcining conditions, is environmentally friendly and can be industrialized easily. The double-casing layer carbon nanometer hollow polyhedron has a wide application prospect in the fields of energy storage, catalysis, photoelectric materials and drug transport.
Description
Technical field
The present invention relates to a kind of is the polyhedral method of templated synthesis bivalve layer carbon hollow nano with metal organic framework compound, belongs to new forms of energy and field of new.
Background technology
Nano material, due to dimensional effect, has and is much better than or physicochemical property that macroscopical block materials does not possess, be thus subject to common people and extensively attract attention.The performance of function nano material depends on its pattern, size and crystal phase structure to a great extent, carries out finely regulating to its microtexture, implementation structure design and controlledly construct the hot fields becoming nanometer material science in recent years and study.
Hollow nanometer material is unique nanostructure that a class has hollow cavity and the continuous shell of nanometer scale thickness.With conventional nano Particle Phase ratio, hollow nanometer material can provide larger specific surface area, shorter lotus matter spreads/transmit length, extra guest materials load space, unique photoelectricity transmission effect etc., thus become the nova in the field of function nano investigation of materials in recent years, be widely applied in fields such as energy storage, catalysis, photoelectric material, drug delivery.
Carbon material has good chemical stability, thermostability, electroconductibility, thermal conductivity, is widely used in the fields such as the energy, catalysis, biologic medical.Hollow nano-carbon material has organically combined the advantage of carbon material and hollow nanostructures, is that a class formation is novel, the function nano material of unique properties.Tradition prepares the method for hollow nano-carbon material mainly based on template, namely utilize metal oxide, silicon-dioxide, polymer microballoon etc. for template, coated organic precursor thereon, obtains hollow nano-carbon material after high-temperature calcination and follow-up template corrosion step.This class methods preparation process is loaded down with trivial details, and nano-form is difficult to a large amount of preparation, and the subsequent corrosion of template often needs poisonous etching agent, thus cannot accomplish scale production.
Summary of the invention
The object of the present invention is to provide a kind of is the polyhedral method of templated synthesis bivalve layer carbon hollow nano with metal organic framework compound.The method should using zinc-base zeolite imidazole ester metal organic framework compound as structured forerunner; bivalve layer carbon hollow nano polyhedron is prepared by high-temperature calcination zeolite imidazole ester metal organic framework compound nanometer nuclear shell nano-structure; external template need not be used; simple and easy to do; environmental protection; energy consumption is low, easy to control, can be used for large-scale production.
The technical solution used in the present invention is: a kind of is the polyhedral method of templated synthesis bivalve layer carbon hollow nano with metal organic framework compound, comprises the steps:
1) zinc salt and organic imidazate are mixed in a solvent, the mol ratio of organic imidazate and zinc salt is (2-100): 1, react 0.5-96 hour under normal pressure, temperature of reaction is 0-200 DEG C, obtains zinc-base zeolite imidazole ester metal organic framework compound nanocrystal; Described zinc salt is at least one in zinc acetate or its hydrate, zinc nitrate or its hydrate, zinc chloride or its hydrate, and zinc solution concentration is 1-10M;
2) zinc-base zeolite imidazole ester metal organic framework compound nanocrystal is mixed in a solvent with cobalt salt, organic imidazate, the mol ratio of organic imidazate and cobalt salt is (2-100): 1,0.5-96 hour is reacted under normal pressure, temperature of reaction is 0-200 DEG C, obtains the metal organic framework compound nano-crystal with core-shell structure body of external sheath cobalt-based zeolite imidazole ester metal organic framework compound; Described cobalt salt is at least one in cobaltous acetate and hydrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and hydrate thereof, cobalt chloride and hydrate thereof, and cobalt salt solution volumetric molar concentration is 1-10M;
3) by the metal organic framework compound nano-crystal with core-shell structure body of external sheath cobalt-based zeolite imidazole ester metal organic framework compound at ambient pressure, calcine in rare gas element in the reactor, calcining temperature is 400-1200 DEG C, calcination time is 0.5-10 hour, obtains bivalve layer carbon/cobalt composite nanometer hollow polyhedron; Described rare gas element is at least one in nitrogen, argon gas or helium;
4) by described bivalve layer carbon/cobalt composite nanometer hollow polyhedron and acid solution reaction, temperature of reaction is 10-180 DEG C, and the reaction times is 0.5-48 hour, with deionized water and washing with alcohol product, obtains bivalve layer carbon hollow nano polyhedron after oven dry; Described acid solution is at least one in nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or hydrofluoric acid.
Described organic imidazate is at least one in phenylimidazole, glyoxal ethyline, 2-nitroimidazole or 2-imidazole formaldehyde, organic imidazate concentration is 2-200M, solvent is at least one in water, methyl alcohol, ethanol, DMF, N-Methyl pyrrolidone and N, N-diethylformamide.
The reactor that described reactor is glass reactor, polytetrafluoroethylliner liner and stainless steel external member seal.
Described bivalve layer carbon hollow nano is polyhedral is of a size of 20nm-10 μm; Bivalve layer carbon hollow nano polyhedron has hollow cavity structure, hollow cavity volume is the 10-95% accounting for bivalve layer carbon hollow nano polyhedron volume, the bivalve polyhedral shell thickness of layer carbon hollow nano is 10-100nm, the bivalve polyhedral shell of layer carbon hollow nano is divided into outer shell and inner shell, outer shell is graphitized carbon, inner shell is decolorizing carbon, and inner shell has micropore and meso-hole structure, and the bivalve polyhedral specific surface area of layer carbon hollow nano is 200-1800m
2g
-1.
Beneficial effect of the present invention is: this with metal organic framework compound be the polyhedral method of templated synthesis bivalve layer carbon hollow nano using zinc-base zeolite imidazole ester metal organic framework compound as structured forerunner, prepare bivalve layer carbon hollow nano polyhedron by high-temperature calcination zeolite imidazole ester metal organic framework compound nanometer nuclear shell nano-structure.The method uses zeolite imidazole ester metal organic framework compound cheap and easy to get to prepare bivalve layer carbon hollow nano polyhedron for structured forerunner.Technique is simple, need not use template, and can carry out finely regulating by the ratio or calcination condition changing zinc/cobalt-based zeolite imidazole ester metal organic framework compound material to shell structure, process environmental protection, is easy to large-scale production.The bivalve layer carbon hollow nano polyhedron of preparation is with a wide range of applications in fields such as energy storage, catalysis, photoelectric material, drug delivery.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of zinc-base zeolite imidazole ester metal organic framework compound material prepared by example 1.
Fig. 2 is that external sheath prepared by example 1 has the stereoscan photograph of the zinc-base zeolite imidazole ester metal organic framework compound nucleocapsid structure of cobalt-based zeolite imidazole ester metal organic framework compound.
Fig. 3 is layer carbon hollow nano polyhedral stereoscan photograph in bivalve prepared by example 1.
Fig. 4 is layer carbon hollow nano polyhedral low power transmission electron microscope photo in bivalve prepared by example 1.
Fig. 5 is layer carbon hollow nano polyhedral high power transmission electron microscope photo in bivalve prepared by example 1.
Fig. 6 is the high power transmission electron microscope photo of bivalve layer carbon hollow nano polyhedron shell structure prepared by example 1.
Embodiment
embodiment 1
(1) prepare the methanol solution (2M) of 30mL zinc nitrate hexahydrate and the methanol solution (12M) of 10mL2-Methylimidazole, at ambient temperature by the two mixing, to stir after 2 minutes standing and reacting 24 hours.After reaction terminates, with methyl alcohol repetitive scrubbing centrifugal 3 times, dry collection and obtain zinc-base zeolite imidazole ester metal organic framework compound material white powder;
(2) by the zinc-base zeolite imidazole ester metal organic framework compound dispersion of materials of preparation in step (1) in the methanol solution (1M) of 30mL Cobaltous nitrate hexahydrate, add in the methanol solution (8M) of 10mL2-Methylimidazole subsequently, at room temperature stir 24 hours.After reaction terminates, with ethanol repetitive scrubbing centrifugal 3 times, dry and collect to obtain cobalt/zinc-base zeolite imidazole ester metallic organic framework nucleocapsid structure red-purple powder;
(3) cobalt step (2) prepared/zinc-base zeolite imidazole ester metallic organic framework Core-shell structure material is heated to 800 DEG C in nitrogen gas stream, and controlling temperature rise rate is 5 DEG C of min
-1, calcination time is 2 hours.After reaction terminates, obtain carbon/cobalt bivalve layer hollow nano polyhedron black powder;
(4) sample dispersion prepared by step (3) in 1M hydrochloric acid soln, 80 DEG C of reacting by heating 24 hours.After reaction terminates, centrifugal to neutral with deionized water repetitive scrubbing, obtain carbon bivalve layer hollow nano polyhedron black powder after oven dry.Hollow Nanoparticles mean outside diameter about 1 μm in powder, shell mean thickness is 120nm, and outer shell is graphitized carbon, and thickness is 40nm, above has shorter carbon nano tube growth, and inner shell is amorphous carbon.Powder specific-surface area detection is 476m
2g
-1, total pore volume is 0.286m
3g
-1.
embodiment 2
(1) prepare the methanol solution (2M) of 30mL zinc nitrate hexahydrate and the methanol solution (12M) of 10mL2-Methylimidazole, at ambient temperature the two is mixed, stir after 2 minutes 120 DEG C of reactions 24 hours.After reaction terminates, with methyl alcohol repetitive scrubbing centrifugal 3 times, dry collection and obtain zinc-base zeolite imidazole ester metal organic framework compound material white powder;
(2) with embodiment 1 step (2);
(3) with embodiment 1 step (3);
(4) with embodiment 1 step (4), Hollow Nanoparticles mean outside diameter about 3 μm in gained black powder, shell mean thickness is 280nm, outer shell is graphitized carbon, thickness is 40nm, above has shorter carbon nano tube growth, and inner shell is amorphous carbon.Powder specific-surface area detection is 638m
2g
-1, total pore volume is 0.428m
3g
-1.
embodiment 3
(1) with embodiment 1 step (1);
(2) by the zinc-base zeolite imidazole ester metal organic framework compound dispersion of materials of preparation in step (1) in the methanol solution (1M) of 10mL Cobaltous nitrate hexahydrate, add in the methanol solution (2M) of 10mL2-Methylimidazole subsequently, at room temperature stir 24 hours.After reaction terminates, with ethanol repetitive scrubbing centrifugal 3 times, dry and collect to obtain cobalt/zinc-base zeolite imidazole ester metallic organic framework nucleocapsid structure red-purple powder;
(3) with embodiment 1 step (3);
(4) with embodiment 1 step (4), in gained black powder, Hollow Nanoparticles mean outside diameter is about 900nm, and shell mean thickness is 100nm, outer shell is graphitized carbon, thickness is 20nm, above has shorter carbon nano tube growth, and inner shell is amorphous carbon.Powder specific-surface area detection is 554m
2g
-1, total pore volume is 0.327m
3g
-1.
Claims (4)
1. be a layer carbon hollow nano polyhedral method in templated synthesis bivalve with metal organic framework compound, it is characterized in that, comprise the steps:
1) zinc salt and organic imidazate are mixed in a solvent, the mol ratio of organic imidazate and zinc salt is (2-100): 1, react 0.5-96 hour under normal pressure, temperature of reaction is 0-200 DEG C, obtains zinc-base zeolite imidazole ester metal organic framework compound nanocrystal; Described zinc salt is at least one in zinc acetate or its hydrate, zinc nitrate or its hydrate, zinc chloride or its hydrate, and zinc solution concentration is 1-10M;
2) zinc-base zeolite imidazole ester metal organic framework compound nanocrystal is mixed in a solvent with cobalt salt, organic imidazate, the mol ratio of organic imidazate and cobalt salt is (2-100): 1,0.5-96 hour is reacted under normal pressure, temperature of reaction is 0-200 DEG C, obtains the metal organic framework compound nano-crystal with core-shell structure body of external sheath cobalt-based zeolite imidazole ester metal organic framework compound; Described cobalt salt is at least one in cobaltous acetate and hydrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and hydrate thereof, cobalt chloride and hydrate thereof, and cobalt salt solution volumetric molar concentration is 1-10M;
3) by the metal organic framework compound nano-crystal with core-shell structure body of external sheath cobalt-based zeolite imidazole ester metal organic framework compound at ambient pressure, calcine in rare gas element in the reactor, calcining temperature is 400-1200 DEG C, calcination time is 0.5-10 hour, obtains bivalve layer carbon/cobalt composite nanometer hollow polyhedron; Described rare gas element is at least one in nitrogen, argon gas or helium;
4) by described bivalve layer carbon/cobalt composite nanometer hollow polyhedron and acid solution reaction, temperature of reaction is 10-180 DEG C, and the reaction times is 0.5-48 hour, with deionized water and washing with alcohol product, obtains bivalve layer carbon hollow nano polyhedron after oven dry; Described acid solution is at least one in nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or hydrofluoric acid.
2. one according to claim 1 take metal organic framework compound as the polyhedral method of templated synthesis bivalve layer carbon hollow nano, it is characterized in that: described organic imidazate is at least one in phenylimidazole, glyoxal ethyline, 2-nitroimidazole or 2-imidazole formaldehyde, organic imidazate concentration is 2-200M, solvent is water, methyl alcohol, ethanol, N, at least one in dinethylformamide, N-Methyl pyrrolidone and N, N-diethylformamide.
3. one according to claim 1 take metal organic framework compound as the polyhedral method of templated synthesis bivalve layer carbon hollow nano, it is characterized in that: the reactor that described reactor is glass reactor, polytetrafluoroethylliner liner and stainless steel external member seal.
4. one according to claim 1 take metal organic framework compound as the polyhedral method of templated synthesis bivalve layer carbon hollow nano, it is characterized in that: described bivalve layer carbon hollow nano is polyhedral is of a size of 20nm-10 μm; Bivalve layer carbon hollow nano polyhedron has hollow cavity structure, hollow cavity volume is the 10-95% accounting for bivalve layer carbon hollow nano polyhedron volume, the bivalve polyhedral shell thickness of layer carbon hollow nano is 10-100nm, the bivalve polyhedral shell of layer carbon hollow nano is divided into outer shell and inner shell, outer shell is graphitized carbon, inner shell is decolorizing carbon, and inner shell has micropore and meso-hole structure, and the bivalve polyhedral specific surface area of layer carbon hollow nano is 200-1800m
2g
-1.
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Application publication date: 20151202 |