CN105460916A - Preparation method of hollow carbon nanospheres-assembled mesoporous carbon fiber material - Google Patents
Preparation method of hollow carbon nanospheres-assembled mesoporous carbon fiber material Download PDFInfo
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C01P2006/00—Physical properties of inorganic compounds
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- C01P2006/16—Pore diameter
Abstract
The invention discloses a preparation method of a hollow carbon nanospheres-assembled mesoporous carbon fiber material and belongs to the technical field of preparation of a mesoporous carbon material. According to the method, nitrilotriacetic acid or soluble metallic ferrous salt or nickel salt are used as raw materials to synthesize a metal complex fiber precursor by a solvothermal method; the complex fiber precursor is calcined under airtight conditions or in argon atmosphere to obtain a core-shell structured nanospheres-assembled carbon/metallic oxide (metal) compound; and the core (metallic oxide (metal)) of the nanospheres in the compound fiber undergoes acid etching to obtain the hollow nanospheres-assembled carbon fiber material rich in carboxy groups. The preparation method has advantages as follows: the process is simple; a solvent can be recovered and recycled; and the preparation cost is low. The prepared carbon material is formed by assembling of hollow nanospheres, has a novel structure and has a good application prospect in fields of adsorption, catalyst carrier and the like.
Description
Technical field
The invention belongs to the preparing technical field of meso-porous carbon material, be specifically related to a kind of preparation method by the assembly mesoporous carbon fibre material of hollow Nano carbon ball.
Background technology
Porous material is that new function material can be used as support of the catalyst, sorbent material etc.Gac has larger specific surface area and stronger adsorptive power due to it, is one of important sorbing material.But in absorbent charcoal material, micropore (aperture <2nm) occupies very large ratio, and relatively larger molecule or compound can not enter in its duct, thus greatly reduce the adsorptive power of gac.
Mesoporous carbon is the novel mesoporous material of a class, is considered to the s-generation mesoporous material after mesopore silicon oxide.Large specific surface area can realize guest materials load effectively, high degree of dispersion, larger aperture be conducive to guest materials assembling and as microreactor, be conducive to reactant and the diffuser efficiency of product in duct simultaneously.There is the C-O chemical bond of a large amount of Gong modifications in mesoporous material surface, they can be used for modifying the channel surfaces of mesoporous carbon.In addition, the duct of mesoporous carbon provides favourable growing space, for the growth of nano material provides possibility for guest materials.
In addition, meso-porous carbon material has high mechanical stability and the feature such as chemical stability, good electroconductibility, makes it have broad application prospects in fields such as absorption, separation, biological medicine, catalysis and electrochemistry.The general template charing legal system that adopts is for mesoporous carbon at present, is divided into hard template method and soft template method two kinds.Mesopore silicon oxide is often selected as hard template, and carbon source is filled in its duct, obtains ordered mesopore carbon through carbonization with after removing silicon template. utilize the self-assembly of amphipathic nature block polymer and resol, with the synthesising mesoporous carbon of soft template method direct carbonization.
Mould the polymkeric substance such as ester, polypropylene with phenolic aldehyde in meso-porous carbon material preparation process to be carbon source, to add program and processing cost that the pore of soft or hard template adds preparation technology undoubtedly; Moreover compared to traditional meso pore silicon oxide material, the mesoscopic structure of this kind of new carbon and pattern are abundant not enough, synthetic method lack innovation and break through, and also very limited to the applied research of material, constrain the practical application of meso-porous carbon material.
Summary of the invention
Object of the present invention aims to provide and is a kind ofly monomer carbon source with small molecules organic polycarboxylic acid, with the method for spontaneous inorganic nanoparticles for the assembly mesoporous carbon fibre material of Template preparation hollow Nano carbon ball, needs to add in addition soft/hard template cause production cost to increase and the comparatively single defect of the meso-porous carbon material structure and morphology prepared for carbon source with organic polymers such as resol to overcome traditional meso-porous carbon material preparation process.
For achieving the above object, the present invention is achieved by the following technical programs.
The invention provides the preparation method of the assembly mesoporous carbon fibre material of a kind of hollow Nano carbon ball, specifically comprise the steps:
(1) add in the isopropanol-water solutions of soluble metallic salt by nitrilotriacetic acid(NTA), in reactor, hydro-thermal leaves standstill, and after being chilled to room temperature, feed liquid obtains metal-nitrilotriacetic acid(NTA) complex precursors fiber after suction filtration drying;
The isopropanol-water solutions concentration of described soluble metallic salt is 0.1mol/L, described soluble metallic salt is 3 ~ 1:1 with the ratio of the amount of substance of nitrilotriacetic acid(NTA), described isopropanol-water mixed liquor volume ratio is 0 ~ 1:1, described hydro-thermal dwell temperature is 160 ~ 220 DEG C, and hydro-thermal time of repose is 10 ~ 24h.
(2) roasting under restricted atmosphere of metal-nitrilotriacetic acid(NTA) complex precursors can be obtained nanocarbon/metal oxide compound (metal) conjugated fibre;
Described restricted atmosphere is under air tight condition or argon gas atmosphere.
(3) nanocarbon/metal oxide compound (metal) conjugated fibre that step (2) obtains is added in pickling solution and leave standstill acid etching, filtration diluted sodium hydroxide solution washs afterwards, be washed with distilled water to filtrate again in neutral, namely final drying obtains the mesoporous carbon filamentary material of hollow nano carbon microsphere assembling;
Described pickling solution is rare sulfuric acid, nitric acid or hydrochloric acid soln, and its concentration is 2mol/L ~ 4mol/L; Described etching time is 4 ~ 12h; Described diluted sodium hydroxide solution concentration is 0.5 ~ 2mol/L; Describedly with a gram quality for nanocarbon/metal oxide compound (metal) conjugated fibre of metering with the volume ratio of the pickling solution measured with milliliter be: 1:20 ~ 100.
Further, in step (1), described soluble metallic salt is ferrous ammonium sulphate or single nickel salt.
Further, the roasting in described step (2) adopts programmed temperature method, and temperature rise rate is 1 ~ 5 DEG C/min, and maturing temperature is 400 ~ 600 DEG C, and roasting time is 3 ~ 6h.
Nano-hollow ball assemble carbon filamentary material formation mechenism of the present invention is as follows: water-soluble metal salt and nitrilotriacetic acid(NTA) form metal-nitrilotriacetic acid(NTA) title complex Precursors of Fibers under solvent thermal condition, title complex Precursors of Fibers in confined conditions or roasting under inert atmosphere, original position formed with nano-metal-oxide (metal) be core, carbon-coating be shell nanometer ball assembling compounding fiber, also namely: precursor fibre pattern basic pattern in roasting process is maintained, fiber base in-vivo metal-title complex decomposition in situ carbonization becomes the nanometer ball of nucleocapsid structure simultaneously.Inorganic core in basic for fiber Component units-core-shell nanospheres is removed by acid etching, forms the carbon fibre material of nano-hollow ball assembling.
Compared with prior art, the beneficial effect that the present invention has is:
1, to have technique simple for preparation method of the present invention, the recyclable recycling of solvent, the cheap and method advantages of environment protection of preparation cost.
2, the carbon fibre material prepared by the present invention is rich in carboxylic group, and overcome the shortcoming of simple carbon-based material light specific gravity and process water body intermiscibility difference, good water body is dispersed, can realize and fully the contacting of guest species.
3, the carbon material prepared by the present invention is assembled by nano-hollow ball, novel structure, has a good application prospect in fields such as absorption, support of the catalyst.
Accompanying drawing explanation
Fig. 1 is (b) X-ray diffractogram after (a), carbon/ferriferous oxide fiber acid etching before embodiment 1 carbon/ferriferous oxide fiber acid etching.
Fig. 2 is scanning electron microscope (SEM) photograph after embodiment 1 carbon/ferriferous oxide fiber acid etching.
Fig. 3 is transmission electron microscope picture (scale label is 200nm) after embodiment 1 carbon/ferriferous oxide fiber acid etching.
Fig. 4 is (b) X-ray diffractogram after (a), carbon/ferriferous oxide fiber acid etching before embodiment 2 carbon/nickel oxide (nickel) fiber acid etching.
Fig. 5 is scanning electron microscope (SEM) photograph after embodiment 2 carbon/nickel oxide (nickel) fiber acid etching.
Fig. 6 is transmission electron microscope picture (scale label is 200nm) after embodiment 2 carbon/nickel oxide (nickel) fiber acid etching.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
(1) 13.9g ferrous sulfate is fully dissolved in the mixed solvent (500mL) of Virahol and water, and wherein the volume ratio of Virahol and water is 0.2:1; 4.8g nitrilotriacetic acid(NTA) is scattered in above-mentioned solution.Mixed solution, in 180 DEG C of standing 24h, cools then feed liquid suction filtration desolvation, and filtrate is reclaimed for subsequent use, 100 DEG C of forced air drying 5h in filter cake air.
(2) step 1 gained dry cake is placed in crucible airtight after, in retort furnace, be warming up to 500 DEG C of roasting 4h with the speed of 2 DEG C/min, be cooled to room temperature.
(3) step (2) product of roasting 10g is added in 200mL, 4mol/L hydrochloric acid soln and leave standstill 10h, filter, first with the washing of 2mol/L sodium hydroxide solution, then be washed with distilled water to filtrate in neutral, with 100 DEG C of forced air drying 5h.Obtain the assembly mesoporous carbon fiber of nano hollow carbon ball.
Typical case adopts the full-automatic diffractometer of X-ray diffraction XpertMPDPhiliphs to characterize product structure, its XRD test result as shown in Fig. 1 a and Fig. 1 b, by inorganic nano core thing phase (Fe after contrast susceptible of proof acid etching
3o
4) disappear.SEM photo adopts JSM-6490LV to analyze, and as shown in Figure 2, display product is threadiness.Its microtexture of JEOL-2010 type TEM (transmission electron microscope) analysis, as shown in Figure 3.Fiber is the filamentary material of nano-hollow ball assembling, and nano-hollow ball is as shown in the illustration of upper left.Adopt N
2adsorption-desorption method measures its meso-hole structure and specific surface thereof, and result shows, this specific fiber surface is 244.5m
2/ g, mesopore size is 12.5nm.
Embodiment 2
(1) 13.1g single nickel salt is fully dissolved in the mixed solvent (500mL) of Virahol and water, and wherein the volume ratio of Virahol and water is 0:1; 3.3g nitrilotriacetic acid(NTA) is scattered in above-mentioned solution.Mixed solution, in 220 DEG C of standing 12h, cools then feed liquid suction filtration desolvation, and filtrate is reclaimed for subsequent use, 100 DEG C of forced air drying 5h in filter cake air.
(2) step 1 gained dry cake is placed in crucible airtight after, in retort furnace, be warming up to 400 DEG C of roasting 6h with the speed of 1 DEG C/min, be cooled to room temperature.
(3) step (2) product of roasting 8g is added in 600mL, 2mol/L sulphuric acid soln and leave standstill 6h, filter, first with the washing of 1mol/L sodium hydroxide solution, then be washed with distilled water to filtrate in neutral, with 100 DEG C of forced air drying 5h.Obtain the assembly mesoporous carbon fiber of nano hollow carbon ball.
Adopt the full-automatic diffractometer of X-ray diffraction XpertMPDPhiliphs to characterize product structure, its XRD test result, as shown in Fig. 4 a and Fig. 4 b, is disappeared by inorganic nano core thing phase (Ni and NiO) after contrast susceptible of proof acid etching.SEM photo adopts JSM-6490LV to analyze, and as shown in Figure 5, is fibrous morphology.Its microtexture of JEOL-2010 type TEM (transmission electron microscope) analysis, as shown in Figure 6, fiber is the filamentary material of nano-hollow ball assembling.Adopt N
2adsorption-desorption method measures its meso-hole structure and specific surface thereof, and result shows, this specific fiber surface is 138.2m
2/ g, mesopore size is 11.4nm.
Embodiment 3
(1) 13.9g ferrous sulfate is fully dissolved in the mixed solvent (500mL) of Virahol and water, and wherein the volume ratio of Virahol and water is 0.5:1; 3.3g nitrilotriacetic acid(NTA) is scattered in above-mentioned solution.Mixed solution, in 200 DEG C of standing 18h, cools then feed liquid suction filtration desolvation, and filtrate is reclaimed for subsequent use, 100 DEG C of forced air drying 5h in filter cake air.
(2) step 1 gained dry cake is placed in crucible airtight after, in retort furnace, be warming up to 600 DEG C of roasting 3h with the speed of 5 DEG C/min, be cooled to room temperature.
(3) step (2) product of roasting 6g is added in 400mL, 3mol/L salpeter solution and leave standstill 8h, filter, first with the washing of 0.5mol/L sodium hydroxide solution, then be washed with distilled water to filtrate in neutral, with 100 DEG C of forced air drying 5h.Obtain the assembly mesoporous carbon fiber of nano hollow carbon ball.
Embodiment 4
(1) 13.1g single nickel salt is fully dissolved in the mixed solvent (500mL) of Virahol and water, and wherein the volume ratio of Virahol and water is 0.8:1; 4.8g nitrilotriacetic acid(NTA) is scattered in above-mentioned solution.Mixed solution, in 160 DEG C of standing 24h, cools then feed liquid suction filtration desolvation, and filtrate is reclaimed for subsequent use, 100 DEG C of forced air drying 5h in filter cake air.
(2) step 1 gained dry cake under argon gas atmosphere, is warming up to 500 DEG C of roasting 4h with the speed of 2 DEG C/min, is cooled to room temperature in retort furnace.
(3) step (2) product of roasting 8g is added in 800mL, 2mol/L hydrochloric acid soln and leave standstill 12h, filter, first with the washing of 2mol/L sodium hydroxide solution, then be washed with distilled water to filtrate in neutral, with 100 DEG C of forced air drying 5h.Obtain the assembly mesoporous carbon fiber of nano hollow carbon ball.
Embodiment 5
(1) 13.9g ferrous sulfate is fully dissolved in the mixed solvent (500mL) of Virahol and water, and wherein the volume ratio of Virahol and water is 1:1; 9.6g nitrilotriacetic acid(NTA) is scattered in above-mentioned solution.Mixed solution, in 220 DEG C of standing 16h, cools then feed liquid suction filtration desolvation, and filtrate is reclaimed for subsequent use, 100 DEG C of forced air drying 5h in filter cake air.
(2) step 1 gained dry cake under argon gas atmosphere, is warming up to 600 DEG C of roasting 3h with the speed of 5 DEG C/min, is cooled to room temperature in retort furnace.
(3) step (2) product of roasting 8g is added in 400mL, 3mol/L salpeter solution and leave standstill 8h, filter, first with the washing of 1mol/L sodium hydroxide solution, then be washed with distilled water to filtrate in neutral, with 100 DEG C of forced air drying 5h.Obtain the assembly mesoporous carbon fiber of nano hollow carbon ball.
Embodiment 6
(1) 13.1g single nickel salt is fully dissolved in the mixed solvent (500mL) of Virahol and water, and wherein the volume ratio of Virahol and water is 0.6:1; 9.6g nitrilotriacetic acid(NTA) is scattered in above-mentioned solution.Mixed solution, in 200 DEG C of standing 24h, cools then feed liquid suction filtration desolvation, and filtrate is reclaimed for subsequent use, 100 DEG C of forced air drying 5h in filter cake air.
(2) step 1 gained dry cake under argon gas atmosphere, is warming up to 400 DEG C of roasting 6h with the speed of 1 DEG C/min, is cooled to room temperature in retort furnace.
(3) step (2) product of roasting 10g is added in 200mL, 4mol/L hydrochloric acid soln and leave standstill 6h, filter, first with the washing of 2mol/L sodium hydroxide solution, then be washed with distilled water to filtrate in neutral, with 100 DEG C of forced air drying 5h.Obtain the mesoporous carbon fiber of nano hollow carbon ball assembling.
Claims (3)
1. a preparation method for the assembly mesoporous carbon fibre material of hollow Nano carbon ball, is characterized in that, comprise the steps:
(1) add in the isopropanol-water solutions of soluble metallic salt by nitrilotriacetic acid(NTA), in reactor, hydro-thermal leaves standstill, and after being chilled to room temperature, feed liquid obtains metal-nitrilotriacetic acid(NTA) complex precursors fiber after suction filtration drying;
The isopropanol-water solutions concentration of described soluble metallic salt is 0.1mol/L, described soluble metallic salt is 3 ~ 1:1 with the ratio of the amount of substance of nitrilotriacetic acid(NTA), described isopropanol-water mixed liquor volume ratio is 0 ~ 1:1, described hydro-thermal dwell temperature is 160 ~ 220 DEG C, and hydro-thermal time of repose is 10 ~ 24h;
(2) roasting under restricted atmosphere of metal-nitrilotriacetic acid(NTA) complex precursors can be obtained nanocarbon/metal oxide compound (metal) conjugated fibre;
Described restricted atmosphere is under air tight condition or argon gas atmosphere;
(3) nanocarbon/metal oxide compound (metal) conjugated fibre that step (2) obtains is added in pickling solution and leave standstill acid etching, filtration diluted sodium hydroxide solution washs afterwards, be washed with distilled water to filtrate again in neutral, namely final drying obtains the mesoporous carbon filamentary material of hollow nano carbon microsphere assembling;
Described pickling solution is rare sulfuric acid, nitric acid or hydrochloric acid soln, and its concentration is 2mol/L ~ 4mol/L; Described etching time is 4 ~ 12h; Described diluted sodium hydroxide solution concentration is 0.5 ~ 2mol/L; Describedly with a gram quality for nanocarbon/metal oxide compound (metal) conjugated fibre of metering with the volume ratio of the pickling solution measured with milliliter be: 1:20 ~ 100.
2. the preparation method of the assembly mesoporous carbon fibre material of hollow Nano carbon ball as claimed in claim 1, it is characterized in that, in step (1), described soluble metallic salt is ferrous ammonium sulphate or single nickel salt.
3. the preparation method of the assembly mesoporous carbon fibre material of hollow Nano carbon ball as claimed in claim 1, it is characterized in that, the roasting in described step (2) adopts programmed temperature method, and temperature rise rate is 1 ~ 5 DEG C/min, maturing temperature is 400 ~ 600 DEG C, roasting time 3 ~ 6h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107159230A (en) * | 2017-05-23 | 2017-09-15 | 武汉工程大学 | A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing and preparation method thereof |
| CN108726508A (en) * | 2018-07-07 | 2018-11-02 | 福州大学 | A kind of low cost prepares the preparation method of graphene hollow fibre |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN112582619A (en) * | 2020-12-14 | 2021-03-30 | 安徽大学 | Preparation method, product and application of nitrogen and oxygen co-doped carbon nanofiber material |
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| CN1834304A (en) * | 2006-03-02 | 2006-09-20 | 上海交通大学 | Method of preparing thin sheet net-like metallic short fiberous material |
| CN1844481A (en) * | 2006-03-09 | 2006-10-11 | 上海交通大学 | Metallization treatment method for short carbon fiber |
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| US4772455A (en) * | 1981-08-05 | 1988-09-20 | Toho Belson Co., Ltd. | Filter |
| JP2004307772A (en) * | 2003-04-03 | 2004-11-04 | Yamaguchi Michiko | Eutectic crystal composition for latent cold heat storage |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159230A (en) * | 2017-05-23 | 2017-09-15 | 武汉工程大学 | A kind of catalyst that low-concentration nitrogen oxide is removed for constant temperature catalyzing and preparation method thereof |
| CN107159230B (en) * | 2017-05-23 | 2019-12-06 | 武汉工程大学 | Catalyst for normal-temperature catalytic removal of low-concentration nitrogen oxides and preparation method thereof |
| CN108726508A (en) * | 2018-07-07 | 2018-11-02 | 福州大学 | A kind of low cost prepares the preparation method of graphene hollow fibre |
| CN108726508B (en) * | 2018-07-07 | 2021-10-29 | 福州大学 | Preparation method for preparing graphene hollow fiber at low cost |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN110127662B (en) * | 2019-05-26 | 2022-02-01 | 天津大学 | Method for preparing porous carbon by using alkali metal-assisted carbonization small-molecule organic solvent |
| CN112582619A (en) * | 2020-12-14 | 2021-03-30 | 安徽大学 | Preparation method, product and application of nitrogen and oxygen co-doped carbon nanofiber material |
| CN112582619B (en) * | 2020-12-14 | 2022-04-12 | 安徽大学 | Preparation method, product and application of nitrogen and oxygen co-doped carbon nanofiber material |
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