CN104759284A - Preparation method of porous carbon-supported nano ferric oxide - Google Patents
Preparation method of porous carbon-supported nano ferric oxide Download PDFInfo
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- CN104759284A CN104759284A CN201510105020.XA CN201510105020A CN104759284A CN 104759284 A CN104759284 A CN 104759284A CN 201510105020 A CN201510105020 A CN 201510105020A CN 104759284 A CN104759284 A CN 104759284A
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- porous charcoal
- iron oxide
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- porous carbon
- carbohydrate
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Abstract
The invention provides a preparation method of porous carbon-supported nano ferric oxide and belongs to the technical field of porous carbon-supported nano ferric oxide materials. The method includes following steps: (1) forming a homogenous molten liquid by means of saccharides, urea and a ferric salt at a certain temperature, so that the ferric salt is uniformly distributed in the liquid; (2) heating the saccharides to carbonize the saccharides to obtain porous carbon while a metal active component is uniformly distributed in the porous carbon; and (3) performing high-temperature thermo-treatment under a protective gas or a reductive atmosphere to obtain the porous carbon-supported nano ferric oxide composite material. The preparation method can be used for supporting various nano metal materials or metal oxide materials with the diameter being 15-1000 nm and with a high monodispersity. By means of adjustment of synthetic conditions, the composition, the crystalline phase and the supporting amount of the nano metals or the metal oxides can be controlled. The preparation method is simple in synthetic route and is low in cost, so that the preparation method has a huge application prospect in industrial catalysis, water treatment and electrochemistry and the like fields.
Description
Technical field
The invention provides a kind of method that one-step method prepares metal-modified porous charcoal loaded with nano iron oxide material, belong to porous charcoal loaded with nano iron oxide material technical field.。
Background technology
Nano material has the peculiar property being obviously different from block materials and individual molecule, such as: skin effect, bulk effect, solidifying sub-dimensional effect and macroscopical tunnel-effect etc., make its electronics, optics, chemical industry, pottery, biology and medical etc. in all have broad application prospects.But nano particle is due to its high surface energy, sintering easily occurs and reunites, therefore nano material often needs carrier, to ensure its monodispersity, reduces the probability that sintering, reunion etc. occur simultaneously.Porous carbon material has flourishing pore structure, very large specific area, more surface compound and very strong adsorption capacity, and also having a series of advantages such as high temperature resistant, acid and alkali-resistance, conduction and heat transfer, is therefore the good carrier of load nano particle.According to the classification of IUPAC (IUPAC), the duct in porous charcoal can be divided into macropore (> 50 nm), mesoporous (2-50 nm) and micropore (< 2 nm).The nano metal of porous charcoal load or oxide material all have broad application prospects in all many-sides such as Industrial Catalysis, water treatment and electrochemistry.
In the preparation method supporting nano material in porous charcoal, what generally adopt is direct dipping process and copolymerization process.Direct dipping process is by porous carbon materials direct impregnation in metal salt solution, and then drying and heat treatment obtain the nano material of porous charcoal load.[Joo S H, Choi S J, Oh I, the et al. (2001) such as Ryoo
. Nature 412 (6843): 169-172.] be incorporated in ordered mesoporous carbon by dipping method of reducing by Pt nanoparticle, the particle diameter obtaining high degree of dispersion is only the platinum grain of 3 nm, makes it be expected to there is application prospect in fuel cell field.Infusion process is widely used, but lacks effective regulation and control for the particle diameter of nano particle, component and distribution in the carrier.Copolymerization process refers to and is filled in foraminous die plate by slaine and carbon source, obtains porous carbon composite material by carbonization and removing template.Ding etc. [Ding J, Chan K Y, Ren J, et al. (2005).
electrochimica Acta 50 (15): 3131-3141.] take SBA-15 as template, methyl alcohol is carbon source, Pt (NH
3)
4(NO
3)
2for slaine, prepare ordered mesoporous carbon/platinum composite, and have studied its electrocatalysis characteristic to oxygen reduction reaction.But preparation method's complexity of copolymerization process is loaded down with trivial details, need pour into carbon source and slaine repeatedly and remove template, the cycle is long, cost is high, and this hinders the scale application of the method undoubtedly.
In recent years, some research groups report and adopt self-assembly method to prepare porous carbon composite easily.Zhao etc. [Liu R., et al. (2007).
chemistry of Materials 20 (3): 1140-1146.] take resol resin as presoma, obtained the TiO of ordered mesoporous carbon load by organic and inorganic self assembly
2with TiC composite.Yao etc. [Yao J., et al. (2009).
carbon 47 (2): 436-444.] take resorcinol as carbon source, directly prepared magnetic separable ordered mesoporous carbon/Ni composite.Ji etc. [Ji Z., et al. (2009).
carbon 47 (9): 2194-2199.] adopt three components altogether assemble method, prepared the ordered mesopore carbon/Ru composite of high-specific surface area, and have studied its catalytic action to benzene hydrogenation.The method is very ripe for the synthesis of silica-base material, but synthesis material with carbon element still needs further further investigation, and the method is difficult to be widely used in the preparation that various charcoal carries metal/metal oxide composite.
Summary of the invention
The object of the invention is to develop a kind of cost low, the catalyst of synthetic route simple porous carbon loaded with nano iron oxide.
The present invention utilizes carbohydrate, urea and molysite to form molten homogeneous liquid at a certain temperature, and molysite is evenly distributed in mixing material.Afterwards, heating makes carbohydrate carbonization obtain porous charcoal, and metal active constituent is evenly distributed in porous charcoal simultaneously, after high-temperature heat treatment, obtains porous charcoal loaded with nano ferric oxide composite material subsequently under protection gas or reducing atmosphere.
Specific embodiment of the invention step is: a kind of method of porous charcoal loaded with nano iron oxide material, carries out according to following step:
A) carbohydrate and urea are pressed the mass ratio of 100:1 ~ 1:10, carbohydrate and molysite mix according to the mass ratio of 100:1 ~ 1:10 to be put in a reservoir, at 100-220 DEG C, stirs 10-60 min, hybrid solid is melted completely, forms uniform solution;
B) the solution heat treatment 8-48h at 120-250 DEG C of temperature will obtained in step a), makes carbohydrate dehydration carbonization obtain dark brown solid; This heat treatment process can be carried out in normal pressure or airtight reactor;
C) by the dark brown solid that obtains in step b) under protective gas atmosphere, at 250-1100 DEG C, heat treatment 2-24 h, obtains the nanometer Fe of porous charcoal load
2o
3material;
D) by the sample A that obtains in step c) at 500 DEG C, under reducibility gas condition, heat treatment 1 h, obtains porous charcoal loading nanometer Fe
30
4material.
Wherein in step (a), carbohydrate is the one in glucose, fructose, sucrose, maltose, lactose, starch and dextrin;
Wherein in step (a), the mass ratio of carbohydrate and urea is 80:1 ~ 1:20; In step (b), the mass ratio of carbohydrate and molysite is 100:1 ~ 1:10;
Protection gas wherein described in step (c) is the one in nitrogen, argon gas, helium; The gaseous mixture of to be hydrogen or carbon monoxide volume fraction be 5 % ~ 10 % of the reducibility gas described in step (d), Balance Air is nitrogen or argon gas.
The present invention utilizes carbohydrate, urea and iron content metal element salt to form molten homogeneous liquid at a certain temperature, and slaine is evenly distributed in mixing material.Afterwards, utilize the method for fabricated in situ, at high temperature make carbohydrate dehydration carbonization, metal component is evenly distributed in carbon carrier simultaneously, obtains charcoal loaded with nano iron oxide finally by high-temperature heat treatment.The present invention may be used for the numerous nano metal of load or oxide material, and it is of a size of 15-1000 nm and monodispersity is high, by regulating synthesis condition, can control the composition of nano metal or oxide, crystalline phase and loading etc.In addition, the pore size of carbon carrier also can be controlled by pulp furnish, reaction pressure and the condition such as temperature, time, and pore-size distribution is from 0.1 nm-10 μm.This synthetic method belongs to anhydrous system, can avoid the synthesis difficulty that prior synthesizing method causes due to metal salt solution hydrolysis.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the porous charcoal load iron oxide that embodiment 3 obtains.
Fig. 2 is the XRD figure of the porous charcoal load iron oxide that embodiment 3 obtains.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited thereto.
Embodiment 1: porous charcoal loaded with nano iron oxide
Synthesis material: glucose, urea, Fe (NO
3)
39H
2o(ferric nitrate)
(1) 100 g glucose, 1 g urea and 1 g Fe (NO is taken
3)
39H
2beaker, in 500 mL beakers, is placed in heatable magnetic stirring apparatus by O afterwards.The temperature of magnetic stirring apparatus rises to 220 DEG C, and Keep agitation 60 min until in beaker medicine formed molten condition.
(2) by melt liquid described in (1), take out a part of solution and put in 120 DEG C of pyroreaction stills, react 48 h sample A and obtain pitchy bulk solids.
(3) with mortar, the sample obtained in (2) is ground, be put in crucible, then at N
2protect lower 1100 DEG C of heat treatment 1 h, obtain porous charcoal loading nanometer Fe
2o
3material.
(4) by the sample A that obtains in (3) at 500 DEG C, 5% H
2/ N
2under condition, heat treatment 1 h, obtains porous charcoal loading nanometer Fe
30
4material.
Embodiment 2: porous charcoal loaded with nano iron oxide
Synthesis material: glucose, urea, Fe (NO
3)
39H
2o(ferric nitrate)
(1) 1 g glucose, 10 g urea and 10 g Fe (NO are taken
3)
39H
2beaker, in 500 mL beakers, is placed in heatable magnetic stirring apparatus by O afterwards.The temperature of magnetic stirring apparatus rises to 100 DEG C, and Keep agitation 10min until in beaker medicine formed molten condition.
(2) by melt liquid described in (1), take out a part of solution and put in 250 DEG C of baking ovens, react 8 h sample A and obtain pitchy bulk solids.
(3) with mortar, the sample obtained in (2) is ground, be put in crucible, then at N
2protect lower 250 DEG C of heat treatment 18 h, obtain porous charcoal loading nanometer Fe
2o
3material.
(4) by the sample A that obtains in (3) at 500 DEG C, 5% H
2/ N
2under condition, heat treatment 6 h, obtains porous charcoal loading nanometer Fe
30
4material.
Embodiment 3: porous charcoal loaded with nano iron oxide
Synthesis material: glucose, urea, Fe (NO
3)
39H
2o(ferric nitrate)
(1) 10 g glucose, 1 g urea and 0.1 g Fe (NO is taken
3)
39H
2beaker, in 100 mL beakers, is placed in heatable magnetic stirring apparatus by O afterwards.The temperature of magnetic stirring apparatus rises to 100 DEG C, and Keep agitation 60 min until in beaker medicine formed molten condition.
(2) by melt liquid described in (1), take out a part of solution to put in 120 DEG C of baking ovens and be designated as sample A, a part of solution adds in pyroreaction still to put in 120 DEG C of baking ovens and is designated as sample B in addition, react 48 h sample A and obtain pitchy bulk solids, sample B obtains pitchy compact solid.
(3) with mortar, the sample A obtained in (2) and sample B is ground respectively, and point be put in two crucibles, then at N
2protect lower 550 DEG C of heat treatments 7 hours, obtain porous charcoal loading nanometer Fe
2o
3material.XRD tests the Fe of show sample A and B
2o
3particle size is respectively 28 nm and 30 nm.BET tests display, and the pore-size distribution of sample A is 50 nm-10 μm, and the pore-size distribution of sample B is 5-50 nm, and specific area is 354m
2/ g.
(4) by the sample A that obtains in (3) at 500 DEG C, 5%H
2/ N
2under condition, heat treatment 6 h, obtains porous charcoal loading nanometer Fe
30
4material, XRD test display Fe
30
4particle size is 34 nm.Fig. 1 is the TEM figure of the porous charcoal load iron oxide that embodiment 3 obtains.Fig. 2 is the XRD figure of the porous charcoal load iron oxide that embodiment 3 obtains.
Claims (6)
1. a method for porous charcoal loaded with nano iron oxide material, is characterized in that carrying out according to following step:
A) carbohydrate and urea are pressed the mass ratio of 100:1 ~ 1:10, carbohydrate and molysite mix according to the mass ratio of 100:1 ~ 1:10 to be put in a reservoir, at 100-220 DEG C, stirs 10-60 min, hybrid solid is melted completely, forms uniform solution;
B) the solution heat treatment 8-48h at 120-250 DEG C of temperature will obtained in step a), makes carbohydrate dehydration carbonization obtain dark brown solid; This heat treatment process can be carried out in normal pressure or airtight reactor;
C) by the dark brown solid that obtains in step b) under protective gas atmosphere, heat treatment 2-24h at 250-1100 DEG C, obtains the nano Fe of porous charcoal load
2o
3material;
D) by the sample A that obtains in step c) at 500 DEG C, under reducibility gas condition, heat treatment 1 h, obtains porous charcoal loading nanometer Fe
30
4material.
2. the method for a kind of porous charcoal loaded with nano iron oxide material according to claim 1, is characterized in that wherein the middle carbohydrate of step (a) is the one in glucose, fructose, sucrose, maltose, lactose, starch and dextrin.
3. the method for a kind of porous charcoal loaded with nano iron oxide material according to claim 1, is characterized in that the mass ratio of the wherein middle carbohydrate of step (a) and urea is 80:1 ~ 1:20.
4. the method for a kind of porous charcoal loaded with nano iron oxide material according to claim 1, is characterized in that the mass ratio of the wherein middle carbohydrate of step (b) and molysite is 100:1 ~ 1:10.
5. the method for a kind of porous charcoal loaded with nano iron oxide material according to claim 1, the protection gas that it is characterized in that wherein described in step (c) is the one in nitrogen, argon gas, helium.
6. the method for a kind of porous charcoal loaded with nano iron oxide material according to claim 1, the reducibility gas that it is characterized in that wherein described in step (d) is hydrogen or carbon monoxide volume fraction is the gaseous mixture of 5% ~ 10%, and Balance Air is nitrogen or argon gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268640A (en) * | 2016-08-29 | 2017-01-04 | 大连理工大学 | A kind of magnetic Nano oil absorption material, Preparation Method And The Use |
| CN107749349A (en) * | 2017-10-19 | 2018-03-02 | 天津工业大学 | A kind of C@F2O3New method prepared by the electrode material of composite construction |
| CN112169803A (en) * | 2020-11-10 | 2021-01-05 | 林爱琴 | Porous carbon-loaded nano metal oxide for water treatment and preparation method thereof |
| CN112744801A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Modified carbon material and preparation process and application thereof |
-
2015
- 2015-03-11 CN CN201510105020.XA patent/CN104759284A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268640A (en) * | 2016-08-29 | 2017-01-04 | 大连理工大学 | A kind of magnetic Nano oil absorption material, Preparation Method And The Use |
| CN107749349A (en) * | 2017-10-19 | 2018-03-02 | 天津工业大学 | A kind of C@F2O3New method prepared by the electrode material of composite construction |
| CN112744801A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Modified carbon material and preparation process and application thereof |
| CN112744801B (en) * | 2019-10-30 | 2023-03-24 | 中国石油化工股份有限公司 | Modified carbon material and preparation process and application thereof |
| CN112169803A (en) * | 2020-11-10 | 2021-01-05 | 林爱琴 | Porous carbon-loaded nano metal oxide for water treatment and preparation method thereof |
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