CN106276856B - A kind of preparation method of porous carbon Quito component nanocomposite - Google Patents
A kind of preparation method of porous carbon Quito component nanocomposite Download PDFInfo
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- CN106276856B CN106276856B CN201610657481.2A CN201610657481A CN106276856B CN 106276856 B CN106276856 B CN 106276856B CN 201610657481 A CN201610657481 A CN 201610657481A CN 106276856 B CN106276856 B CN 106276856B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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Abstract
The invention discloses a kind of preparation methods of porous carbon Quito component nanocomposite, comprising the following steps: is pre-processed the natural biologic material with fine graded porous structure to be used as template；By the step impregnation and atmosphere calcination processing of metal salt solution, it is matrix and the multicomponent composite materials for loading heterogeneity nano unit that the porous carbon with biological template fine hiberarchy, which is made,.Template used by the method for the present invention is from the natural biologic material being easy to get extensively and can directly provide carbon source, by selecting different metal salt solutions, the technological parameter for regulating and controlling different dipping process and calcination process may be implemented to control the multicomponent mixture of final composite material and fine micro-nano hierarchical structure.Preparation method of the invention is easy to operate, low in cost, and flexibly controllable, obtained by nanocomposite have broad application prospects in fields such as catalysis, sensing, lithium electricity.
Description
Technical field
The present invention relates to a kind of preparation methods of multicomponent nanocomposite composite material, more particularly to one kind is with classifying porous
The carbon material of structure carries out compound institute as matrix, dissimilar metals and metallic compound nano structure on porous carbon base body
The preparation method of porous carbon Quito component nanocomposite of formation, belongs to C-base composte material technical field.
Background technique
The industrial technology of modern civilization provides sufficient product for human lives and brings great convenience, Que Yecun
In the environmental problems such as air pollution, water pollution, efficiency of energy utilization be low.How to prepare being capable of efficient detection gas, rush
Environment-friendly materials, the raising efficiency of energy utilization effectively degraded into pollutant, especially realize material when facing a variety of environmental problems
The function of material is integrated, is a kind of process that this current research field is badly in need of.
For being applied in many multi-functional nanometer materials of environmental problem, usually because component single and in practical application
During encounter many obstacles.With semiconductor material SnO2For, it applies in sensory field, because of SnO2Activity is not high to keep its right
When some gases are detected, there are significant limitations for Gas-sensing measurment and selectivity, thus the range limited its application
And depth；It applies in photocatalysis field, due to its forbidden bandwidth 3.6eV, belongs to wide band gap semiconducter, it can only be using in sunlight
The ultraviolet portion less than 4%, to seriously constrain the performance of photocatalysis performance.Therefore, it is necessary to pass through material composition
It is compound, preparation various ingredients intercouple the nano material coexisted.
On the other hand, there is high-specific surface area, and the classification that can provide more active sites and active transmission duct is more
Pore structure is conducive to improve sensing property, adsorption capacity and the catalytic activity etc. of material, therefore obtaining has micro-nano classifying porous
Structure is to promote the important channel of composite property.For the preparation of classifying porous material, currently used method, such as: gas
Phase sedimentation, solution vapour deposition method, method of electrostatic spinning etc. have been carried out some trials and exploration.However, current these preparation methods
It generally requires to carry out under conditions of relatively harsh by specific experimental facilities with means, preparation process is more difficult to control, especially
It is difficult to realize the compound of effective control to fine graded porous structure and various ingredients.
Moreover, porous C-base composte material due to excellent capacitive properties, lithium electrical property, sensing property etc. more
Field has significant application value and increasingly attracts extensive attention and pay attention to.Firstly, carbon base body can be used as the height of transmission electronics
Fast channel promotes the performance that energy and information are transmitted in electronic transmission process.Secondly, carbon relies on its high temperature resistant, low-density and heat
The small equal excellent properties of the coefficient of expansion, allow the micro-nano structure of material to keep relative stability, and provide life for other components material
Long matrix.Furthermore component modification is implemented in the introducing of carbon, so that the performance to composite material improves.It finds, closes through retrieval
There are many patent disclosures in c-based nanomaterial, such as a kind of entitled " manganese oxide/carbon/carbon nanotube of publication number CN105702923A
In the patent of nano-hybrid material and its preparation method and application ", manganese oxide precursor solution is dispersed in thermosetting resin list
In body solvent, which can be used as carbon source simultaneously；Then carbon nanotube is introduced, the solid after solidifying by double bond is through powder
It is obtained after broken, high-temperature calcination, but this method cannot provide fine hole configurations；Publication number CN102951677A is entitled
" based on aumospheric pressure cvd method preparation stannic oxide micro-nano rice material method " patent in, prepare carbonaceous material with
The process of nanometer titanium dioxide tin composite is complicated, and lacks apparent advantage in application aspect.
Summary of the invention
For the prior art compeling in the deficiency and porous C-base composte material for preparing fine micro-nano structure composite material
Application demand is cut, preparation method of the invention selects the biomaterial with particular hierarchical porous structure type as carbon base body
Source is based on biological template method, step impregnation technology and atmosphere calcine technology, first to natural biological by taking rape pollen as an example
Template carries out pre-treatment and activation, then through the multiple impregnation of substep, then carries out control climate calcination processing, prepares porous carbon-based
Multicomponent nanocomposite composite material.Preparation method technical process of the invention is simple, high reliablity, low in cost, it can be achieved that different
Kind metal and metal compound material are effective compound on classifying porous carbon base body, and by adjusting dipping process and can forge
The technological parameter of burning process realizes high-performance porous carbon with features such as the ingredient and the micro-nano hierarchical structures that control final composite material
The controllable preparation of Quito component nanocomposite.Porous carbon base multicomponent nanocomposite made from preparation method according to the present invention is multiple
Condensation material has broad application prospects in fields such as air-sensitive, photocatalysis, battery, super capacitors.
The specific technical solution of the present invention is as follows:
A kind of preparation method of porous carbon Quito component nanocomposite, comprising the following steps:
1) natural biologic material with porous structure is selected to pre-process as template, and to template；
2) template is sequentially placed into the first maceration extract and the second maceration extract and carries out multiple step impregnation, taken after the completion of dipping
It template and is cleaned and is dried out；
3) template is subjected to atmosphere calcining, porous carbon Quito component nanocomposite is made.Multicomponent refers to different
Metal simple-substance and metallic compound.
Preferably, template refers to fine graded porous structure and can provide abundant carbon source and be used to prepare porous carbon base body
Natural biologic material.For example, pollen.
Preferably, pretreatment refers to: template being placed in ethyl alcohol and carries out sonic oscillation or stir process, then cleans and dries.
Pretreatment dredges its porous structure, and obtain active bio to remove the minerals impurity in natural biologic material
Template.Pretreated purpose is active natural biomaterial, so pretreated mode is without being limited thereto, as long as being able to achieve activation
Method.
Preferably, the first maceration extract refers to the inorganic salt solution of precious metal ion, the first maceration extract be concentration 0.05~
The ethanol solution or aqueous solution of 0.5mmol/L.It is highly preferred that precious metal ion includes one of palladium, platinum, gold, silver, copper or several
The combination of kind.
Preferably, the second maceration extract refers to the inorganic salt solution of transition metal ions, the second maceration extract be concentration 0.01~
The ethanol solution or aqueous solution of 0.1mol/L.It is highly preferred that the inorganic salts of transition metal ions include tin, antimony, zinc, iron, cobalt,
The combination of one or more of nickel, indium, the nitrate of cerium, hydrochloride, sulfate, sulfide.
Preferably, the atmosphere that atmosphere calcining uses is the mixed gas of air, nitrogen or oxygen and nitrogen.Mixed gas
The volume ratio range of middle oxygen and nitrogen is 20:80~0:100.The calcine technology of atmosphere calcining is: 1~10 DEG C of heating rate
400~700 DEG C are risen to be calcined.
Detailed description of the invention
Fig. 1 is in the embodiment of the present invention 1 using pollen as porous carbon Quito component nanocomposite made from template
SEM figure；
Fig. 2 is in the embodiment of the present invention 1 using pollen as porous carbon Quito component nanocomposite made from template
HRTEM figure.
Specific embodiment
In embodiments of the present invention, after carrying out pre-treatment and activation to biological template, using step impregnation, then it is cleaned, dry
It is dry, finally using processing steps such as atmosphere calcinings, prepare porous carbon Quito component nanocomposite.
Embodiment 1
Rape pollen by purchase from Wang Shi honey garden takes 5g to be dissolved in about 100ml dehydrated alcohol, the ultrasound vibration at 40kHz
It cleans after swinging 5min, then is cleaned after sonic oscillation 25min at 40kHz, filtered after room temperature 1000r/min magnetic agitation 5min,
Cleaning 2 times repeatedly, spontaneously dries.Take 0.05mmol PdCl2It is molten that powder is dissolved in formation supersaturation in 100ml dehydrated alcohol
Liquid adjusts its pH=6, then filters, and upper layer is taken to clarify saturated solution, is single-steeping solution.The pollen pre-processed is soaked
Enter in the above single-steeping liquid, with 1000r/min magnetic agitation 15h, then filters, cleans, is dry, being protected from light kept dry is one
Secondary impregnation product.Single-steeping product is immersed to the SnCl of 0.04mol/L4·5H2In O ethanol solution, with 1000r/min magnetic force
8h is stirred, then filters, clean, is dry, being protected from light kept dry is double-steeping product.It is in volume ratio by double-steeping product
The N of 1:12-O2Under atmosphere, 400 DEG C of calcining 2h are raised to 2 DEG C/min heating rate, then cool to room temperature, preparation classification with the furnace
Porous carbon Quito component nanocomposite, wherein carbon base body remains the graded porous structure of pollen template, metal simple-substance Pd
Crystallite dimension is 2.5nm, and PdO crystallite dimension is 2nm, SnO2Crystallite dimension is 4.5nm, and various nanocrystals are equal on carbon base body
Even distribution.
SEM and EDS test and analysis have been done to the present embodiment obtained product, as a result see the table below the figure of 1 and Figure of description
1.Fig. 1 is to scheme in the present embodiment by the SEM of porous carbon Quito component nanocomposite made from template of pollen；Table 1 is this
Using pollen as the EDS power spectrum result of Fig. 1 of porous carbon Quito component nanocomposite made from template in embodiment.
Table 1
Embodiment 2
Rape pollen by purchase from Wang Shi honey garden takes 5g to be dissolved in about 100ml dehydrated alcohol, the ultrasound vibration at 40kHz
It cleans after swinging 5min, then is cleaned after sonic oscillation 25min at 40kHz, taken out after room temperature 1000r/min magnetic agitation 5min later
Filter, cleaning 2 times repeatedly, spontaneously dry.Take 0.05mmol PdCl2Powder, which is dissolved in 100ml dehydrated alcohol, forms satiety
And solution, its pH=8 is adjusted, is then filtered, upper layer is taken to clarify saturated solution, is single-steeping solution.The flower that will have been pre-processed
Powder immerses in the above single-steeping liquid, with 1000r/min magnetic agitation 15h, then filters, cleans, is dry, being protected from light kept dry
For single-steeping product.Single-steeping product is immersed to the SnCl of 0.04mol/L4·5H2In O ethanol solution, with 1000r/min
Then magnetic agitation 8h is filtered, is cleaned, is dry, being protected from light kept dry is double-steeping product.By double-steeping product in nitrogen
Under protection, 500 DEG C of calcining 2h are raised to 2 DEG C/min heating rate, then cool to room temperature, preparation classification under nitrogen protection with the furnace
Porous carbon Quito component nanocomposite, wherein carbon base body remains the graded porous structure of pollen template, metal simple-substance Pd
Crystallite dimension is 3nm, and PdO crystallite dimension is 2nm, SnO2Crystallite dimension is 5nm, and various nanocrystals uniformly divide on carbon base body
Cloth.
Embodiment 3
Rape pollen by purchase from Wang Shi honey garden takes 5g to be dissolved in about 100ml dehydrated alcohol, the ultrasound vibration at 40kHz
It cleans after swinging 5min, then is cleaned after sonic oscillation 25min at 40kHz, taken out after room temperature 1000r/min magnetic agitation 5min later
Filter, cleaning 2 times repeatedly, spontaneously dry.Take 0.05mmol PdCl2Powder, which is dissolved in 100ml dehydrated alcohol, forms satiety
And solution, its pH=8 is adjusted, is then filtered, upper layer is taken to clarify saturated solution, is single-steeping solution.The flower that will have been pre-processed
Powder immerses in the above single-steeping liquid, with 1000r/min magnetic agitation 15h, then filters, cleans, is dry, being protected from light kept dry
For single-steeping product.Single-steeping product is immersed to the SnCl of 0.04mol/L4·5H2In O ethanol solution, with 1000r/min
Then magnetic agitation 8h is filtered, is cleaned, is dry, being protected from light kept dry is double-steeping product.By double-steeping product in volume
Than the N for 2:12-O2Under atmosphere, 600 DEG C of calcining 2h are raised to 2 DEG C/min heating rate, then cool to room temperature with the furnace, prepared
Graded porous carbon Quito component nanocomposite, wherein carbon base body remains the graded porous structure of pollen template, metal list
Matter Pd crystallite dimension is 3nm, and PdO crystallite dimension is 2.5nm, SnO2Crystallite dimension is 5.5nm, and various nanocrystals are in carbon base body
On be uniformly distributed.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (6)
1. a kind of preparation method of porous carbon Quito component nanocomposite, which comprises the following steps:
1) selection has fine graded porous structure and can provide the natural biological material that abundant carbon source is used to prepare porous carbon base body
Material is used as template, and pre-processes to the template, and the natural biologic material is pollen；The pretreatment refers to: by institute
It states template and is placed in progress sonic oscillation or stir process in ethyl alcohol, then clean and dry；
2) template is sequentially placed into the first maceration extract and the second maceration extract and carries out multiple step impregnation, taken after the completion of dipping
It the template and being cleaned and is dried out, first maceration extract refers to the inorganic salt solution of precious metal ion, described first
Maceration extract is the ethanol solution or aqueous solution of 0.05~0.5mmol/L of concentration, and the second maceration extract refers to the nothing of transition metal ions
Machine salting liquid, second maceration extract are the ethanol solution or aqueous solution of 0.01~0.1mol/L of concentration；
3) template is subjected to atmosphere calcining, porous carbon Quito component nanocomposite is made.
2. a kind of preparation method of porous carbon Quito component nanocomposite as described in claim 1, which is characterized in that institute
State the combination that precious metal ion includes one or more of palladium, platinum, gold, silver, copper.
3. a kind of preparation method of porous carbon Quito component nanocomposite as described in claim 1, which is characterized in that institute
The inorganic salts for stating transition metal ions include tin, antimony, zinc, iron, cobalt, nickel, indium, the nitrate of cerium, hydrochloride, sulfate, vulcanization
The combination of one or more of object.
4. a kind of preparation method of porous carbon Quito component nanocomposite as described in claim 1, which is characterized in that described
The atmosphere that atmosphere calcining uses refers to the mixed gas of air, nitrogen or oxygen and nitrogen.
5. a kind of preparation method of porous carbon Quito component nanocomposite as claimed in claim 4, which is characterized in that described
The volume ratio range of oxygen and nitrogen is 20:80~0:100 in mixed gas.
6. a kind of preparation method of porous carbon Quito component nanocomposite as described in claim 1, which is characterized in that described
The calcine technology of atmosphere calcining is: 1~10 DEG C of heating rate rises to 400~700 DEG C and is calcined.
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| CN108878909A (en) * | 2018-07-13 | 2018-11-23 | 中南大学 | A kind of three-dimensional porous composite material and preparation method and application based on biomass |
| CN111161904B (en) * | 2020-01-04 | 2021-01-12 | 浙江大学 | Preparation method of light high-conductivity porous conductive agent and application of light high-conductivity porous conductive agent in battery electrode |
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| CN101249952B (en) * | 2008-03-27 | 2010-06-16 | 上海交通大学 | Method for preparing self-doping nitrogen grading porous oxide by using biomass template |
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