CN102923687A - Middle-pore carbon material and its preparation method - Google Patents

Middle-pore carbon material and its preparation method Download PDF

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CN102923687A
CN102923687A CN2011102295051A CN201110229505A CN102923687A CN 102923687 A CN102923687 A CN 102923687A CN 2011102295051 A CN2011102295051 A CN 2011102295051A CN 201110229505 A CN201110229505 A CN 201110229505A CN 102923687 A CN102923687 A CN 102923687A
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magnesium oxide
aldehyde compounds
mesoporous carbon
obtains
template
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CN102923687B (en
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朱月香
隗罡
王羽
谢有畅
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BEIJING BODA GREEN HIGH TECHNOLOGIES Co Ltd
Peking University
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BEIJING BODA GREEN HIGH TECHNOLOGIES Co Ltd
Peking University
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Abstract

The invention discloses a middle-pore carbon material and its preparation method. The method comprises the following steps: 1, uniformly mixing an aldehyde compound, a phenolic compound and a magnesium oxide template, and carrying out a polymerization reaction to obtain resin coated magnesium oxide; 2, carbonizing the resin coated magnesium oxide obtained in step 1 through heating in an inert atmosphere to obtain carbon coated magnesium oxide; and 3, dissolving magnesium oxide through uniformly mixing the carbon coated magnesium oxide obtained in step 2 with an acid in order to obtain the middle-hole carbon material. The highest specific surface area and the highest middle-pore pore volume of the middle-pore carbon material provided by the invention can exceed 2600m<2>/g and 5.5cm<3>/g respectively under a condition that the middle pore rate of the middle-pore carbon material exceeds 95%; and the method has obvious advantages unmatched by known technologies in the regulation of the pore diameter distribution, the pore wall thickness and the like of the middle-pore carbon material, and deserves the wide popularization and application in the catalytic field, the adsorption field, the electrode material field and the like.

Description

Mesoporous Carbon Materials and preparation method thereof
Technical field
The invention belongs to advanced nano-porous materials and technical field, be specifically related to a kind of Mesoporous Carbon Materials and preparation method thereof.
Background technology
Hole in the porous carbon material according to the classification of International Union of Pure and Applied Chemistry(IUPAC) (IUPAC) can be divided into micropore (aperture＜2nm), mesopore (2～50nm) and macropore (＞50nm).Traditional absorbent charcoal material pore size distribution mainly is in range of micropores, and specific surface area is generally at 500-1500m 2/ g, pore volume is generally less than 1cm 3/ g, its application in emerging high-tech area has been subject to the too small restriction in aperture.
After nineteen seventies, occurred adopting chemical activation method take the potassium hydroxide activation method as representative to prepare the technology of so-called super-activated carbon (Super activated carbon), and realized industrial production in the eighties.The advantage of chemical activation method is can improve the specific surface area of porous carbon material (generally can reach 2000-4000m 2/ g), improve to a certain extent the mesopore ratio simultaneously.Produce a large amount of environmental problems during the outstanding problem of potassium hydroxide chemical activation method is to produce, a large amount of simple substance potassium overflow activation furnace and can cause huge potential safety hazard under the high temperature simultaneously.In addition, chemical activation method is limited to the ability of regulation and control of holes of products structure, product is difficult to avoid having a large amount of micropores, even the highest mesoporous also was no more than 83% after for example the porous carbon with high specific surface area of patent CN1583550A preparation passed through the re-activation reaming, Zong pore volume is no more than 2.4cm 3/ g.
Since nineteen ninety-nine, and the ordered mesoporous carbon of template synthesis (J.Phys.Chem.B, 1999,103 (37), 7743-7746) cause extensive concern at scientific research field.Template can roughly be divided into two kinds of hard template method and soft template methods again.It is template that hard template method adopts the ordered mesoporous silicon oxide usually, and its advantage is the Mesoporous Carbon Materials high-sequential that makes, and pore size distribution can be relatively concentrated.Its shortcoming is that process is loaded down with trivial details, and cost is very high, removes hydrofluoric acid tool severe corrosive and the volatility of silicon oxide template, and easily contaminate environment is difficult to realize industrialization.
Soft template method can be described as again the supramolecule self-assembly method, because it does not need to use and remove the silicon oxide template, hard template method can reduce production stage relatively, saves cost.But soft template method need use the high-molecular block copolymer nonionogenic tenside as soft template equally, and this soft template use of after the charing stage, can't regenerating, its higher price still is the bottleneck that determines product mesoporous carbon cost, has restricted the prospect of the method large-scale application.And it is serious that soft template method exists the carbonization process skeleton to shrink, and obtains ordered mesoporous carbon material pore volume shortcoming on the low side.For example the ordered mesoporous carbon material pore volume that makes of patent CN101955180A is mostly only at 0.30cm 3/ g-0.45cm 3Between/g the scope.For example the ordered mesoporous Carbon Materials that makes of patent CN101823706A sees that from the TEM photo its orderly aperture can surpass 10nm again, but pore wall thickness is between the scope of 5-25nm, and pore volume is also just at 0.3-1cm 3Between/the g.
Charcoal gas (freezing) gel of organic gas (freezing) gel charring preparation also is a kind of Mesoporous Carbon Materials, and specific surface area generally is 200-1100m 2/ g, porosity is high, and typical pore dimension is less than 50nm, and the poor controllability of pore size distribution is just opposite with the characteristics of ordered mesoporous carbon.Need the special dry means such as supercritical drying or lyophilize because prepare organic gas (freezing) gel, equipment cost is high, complex process, and its commercial applications is very limited.
In sum, except hard template method, there is obvious weakness in other mesoporous carbon preparation method aspect the controllability of pore size distribution.And for the expensive of ordered mesoporous silicon oxide template and the shortcoming that needs hydrofluoric acid removal template, the research that non-oxide silicon hard template prepares mesoporous carbon also has some reports, more representational is rice wall doffer (Michio Inagaki) etc. prepares mesoporous carbon about using magnesium oxide template research (Carbon, 2010,48 (10), 2690-2707).Their method is that using magnesium oxide template or magnesium oxide precursor mix according to different ratios with a kind of carbon precursor, through 700-1000 ℃ of charing under the inert atmosphere protection, removes using magnesium oxide template with diluted acid again and obtains mesoporous carbon.The high-specific surface area that the method obtains mesoporous carbon can reach 2000m 2/ g.
Using magnesium oxide template adopts dual mode to obtain: directly adopt the roughly reagent oxidation magnesium about 100nm of a kind of particle diameter 1.; 2. adopt to be heated and easily resolve into magnesian salt compounds.These magnesium salts comprise: magnesium acetate, magnesium citrate, Menesia and magnesium basic carbonate.
Carbon precursor can be divided three classes: 1. superpolymer, comprise: polyvinyl alcohol (PVA), hydroxypropylcellulose (HPC), polyethylene terephthalate (PET), polyvinylpyrrolidone (PVP), polyacrylamide (PAM) and polyimide (PI) (poly-pyromellitic dianhydride (PMDA)/4,4 '-benzidine ether (ODA)); 2. trimethylolmelamine (TMM); 3. coal tar pitch.
Using magnesium oxide template or template precursor are divided into two kinds with the hybrid mode of carbon precursor: 1. powder mixes; 2. solution mixes.The carbon layer that forms on the charing rear oxidation magnesium template can be thought to be dominated by blending ratio within the specific limits substantially, and magnesium oxide ratio still less forms thicker carbon layer.
The pore size distribution of the porous charcoal product that powder mix reagent magnesium oxide/PVA obtains after passing through charing and going template is take micropore as main.The pore size distribution of the porous charcoal product that reagent oxidation magnesium/HPC and reagent oxidation magnesium/PET obtains is take mesopore as main, but the BET specific surface area is on the low side, does not surpass 800m 2/ g.
Coal tar pitch is because widely apply and have high carbon yield at carbon industry, thus also be used as carbon precursor studied (Carbon, 2007,45,1121-1124).The product pore size distribution of powder mixing magnesium acetate/coal tar pitch porous charcoal processed is take mesopore as main, and the optimum mixture ratio example is magnesium oxide/coal tar pitch=7/3, BET specific surface area 1187m 2/ g, the about 3.1cm of maximum mesopore volume 3/ g, the about 13nm in most probable aperture.The product pore size distribution of powder mixing magnesium citrate/coal tar pitch porous charcoal processed is also take mesopore as main, and the blending ratio of BET specific surface area maximum is that magnesium oxide/coal tar pitch equals 10/0, the carbonizing production of pure magnesium citrate namely, the about 1600m of BET specific surface area 2/ g, maximum mesopore volume are less than magnesium acetate/coal tar pitch porous charcoal processed, and 1.3cm only has an appointment 3/ g, the about 5nm in most probable aperture.
The porous charcoal product that powder mixing magnesium acetate/PVA obtains after passing through charing and going template contains more micropore, poor effect.The temperature rise rate of 10 ℃/min causes higher micropore specific area than the temperature rise rate of 5 ℃/min.
The pore size distribution of the porous charcoal product that powder mixing magnesium citrate/PVA obtains after passing through charing and going template is take mesopore as main.Blending ratio magnesium oxide/PVA is little greater than the specific surface area difference more than 5/5, the about 1.7cm of maximum mesopore volume 3/ g, the about 5nm in most probable aperture.
Pure Menesia is about 26% in the carbon yield of 900 ℃ of charings, almost the same with magnesium citrate (Carbon, 2007,45,209-211).The about 1400m of porous charcoal product high specific surface-area that Menesia/PVA obtains after passing through charing and going template 2/ g, most probable aperture 2-4nm, pore ratio are higher than magnesium citrate/PVA porous charcoal.
Magnesium acetate, magnesium citrate and PVA are water-soluble, therefore mix by different ratios with the PVA aqueous solution with the magnesium acetate aqueous solution or the magnesium citrate aqueous solution, and dry afterwards 900 ℃ of charings are carried out research as the example that solution mixes.The BET specific surface area of solution mixing magnesium acetate/PVA (MgO/PVA ratio 7/3) porous charcoal product can be up to 1800m 2/ g is far above the 1080m of powder mixing magnesium acetate/PVA 2/ g.As seen solution mixing magnesium acetate/PVA and powder mixed phase ratio mix more evenly, and successful will be got well.Two kinds of different hybrid modes are little on the impact of magnesium citrate/PVA porous charcoal final product processed, and reason may be interpreted as the magnesium citrate/product char of PVA charing and derives from simultaneously the charing of PVA and citric acid, so the impact that whether mixes is not very large.
The advantage of using magnesium oxide template legal system mesoporous carbon mainly contains 3 points: 1. template magnesium oxide is easy to be removed by non-severe corrosive diluted acid, comprises organic monoacid such as acetic acid or citric acid etc.2. template magnesium oxide can be used as template after by dissolvings such as acetic acid or citric acids and recycles, and effectively saves cost, environmental contamination reduction.3. the size of mesopore and volume can be by the magnesian size regulation and control of template in the product.For example, it is the template precursor that the mesoporous carbon of preparation mesopore aperture 2-4nm can be selected Menesia, and it is the template precursor that the mesoporous carbon about the 5nm of mesopore aperture can be selected magnesium citrate, and it is the template precursor that the mesoporous carbon about the 13nm of mesopore aperture can be selected magnesium acetate.
Still there are some shortcomings in rice wall doffer's etc. using magnesium oxide template carbon precursor hybrid system aspect the controllability of preparation Mesoporous Carbon Materials except above advantage.For example: 1. rice wall method provides more effective control measures to the porous charcoal of preparation mesopore pore size distribution in the 2nm-15nm scope, namely selects respectively Menesia, magnesium citrate or magnesium acetate to regulate and control the aperture as the template precursor.But the method fails to provide effective example to study to the porous charcoal in the preparation mesopore pore size distribution larger mesopore of tool aperture in the 20nm-50nm scope.2. Menesia and the magnesium citrate template precursor itself of the use of rice wall method just have quite high high temperature carbon yield, even cause not mixing any other carbon precursor, the mesopore wall thickness that pure Menesia or magnesium citrate charing make final porous charcoal finished product also can only be nano level thickness, is subject to method itself to the regulation and control of thinner hole wall direction and limits completely.This also is to adopt the high-specific surface area of porous charcoal of Menesia and the preparation of magnesium citrate template precursor can not surpass 1600m in its paper 2/ g, the reason place for preparing the high-specific surface area of porous charcoal less than magnesium acetate template precursor.
Summary of the invention
The present invention acts on and implements the theory that Surface molecular engineering is learned, and has proposed the concept of solid surface catalytic polymerization.Method of the present invention can be summarized as the method that the charing of using magnesium oxide template surface aggregate prepares Mesoporous Carbon Materials.So the purpose of this invention is to provide a kind of Mesoporous Carbon Materials and preparation method thereof.
The present invention has utilized using magnesium oxide template to possess alkalescence, but the characteristics of catalysis phenolic compound and aldehyde compound polymerization, use micromolecular phenols and aldehyde compound to be raw material, catalytic polymerization occurs in the surface at using magnesium oxide template, give birth to lamellar resol, through high temperature carbonization, remove two steps of template again, finally obtain high performance thin-walled Mesoporous Carbon Materials.The method is following method one or method two, and wherein, method one comprises the steps:
1) liquid aldehyde compounds, phenolic compound and using magnesium oxide template mixing are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
Perhaps, solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and using magnesium oxide template mixing in solvent are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated carries out charing after being heated up by room temperature, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal dissolves magnesium oxide with sour mixing, obtains described Mesoporous Carbon Materials.
Method two comprises the steps:
1) liquid aldehyde compounds, phenolic compound and using magnesium oxide template mixing are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
Perhaps, solid aldehyde compounds or liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and using magnesium oxide template mixing in solvent are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated carries out charing after being heated up by room temperature, obtains the magnesium oxide that charcoal coats;
3) with described step 2) gained the charcoal magnesium oxide, described liquid aldehyde compounds and the described phenolic compound mixing that coat carry out described polyreaction, react the complete magnesium oxide that obtains the coating of resin secondary;
Perhaps, with described step 2) gained the charcoal magnesium oxide, described solid aldehyde compounds or the described liquid aldehyde compounds that coat or gaseous aldehyde compounds and described phenolic compound mixing in described solvent carry out polyreaction, react the complete magnesium oxide that obtains the coating of resin secondary;
4) in inert atmosphere, with described step 3) magnesium oxide that coats of gained resin secondary carries out charing after being heated up by room temperature, obtains the magnesium oxide that the charcoal secondary coats;
5) with described step 4) magnesium oxide that coats of gained charcoal secondary dissolves magnesium oxide with sour mixing, obtains described Mesoporous Carbon Materials.
In above-mentioned two methods, described liquid aldehyde compounds all is selected from least a in acetaldehyde, propionic aldehyde, butyraldehyde, hexanal, propenal, crotonic aldehyde, furfural, phenyl aldehyde, phenylacetic aldehyde, phenylacrolein, salicylic aldehyde, oxalic dialdehyde and the paraldehyde, at least a in preferred furfural and the phenyl aldehyde;
Described solid aldehyde compounds all is selected from least a in trioxymethylene, Paraformaldehyde 96, terephthal aldehyde and the Vanillin, at least a in preferred trioxymethylene and the Paraformaldehyde 96;
Described gaseous aldehyde compounds all is selected from least a in formaldehyde and the acetaldehyde, preferred formaldehyde;
Described phenolic compound all is selected from least a in phenol, dihydroxy-benzene, benzenetriol, cresols, xylenol, tert.-butyl phenol, chavicol, thymol, methoxyl group phenol, naphthols and the cardanol, at least a in preferred phenol, dihydroxy-benzene and the cresols;
Described solvent all is selected from least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, n-hexyl alcohol, hexalin, ethylene glycol, propylene glycol, ether, tetrahydrofuran (THF), acetone, butanone, furfural, benzene,toluene,xylene, trimethylbenzene, ethylbenzene and the dimethyl sulfoxide (DMSO), at least a in preferred alcohol, the trimethyl carbinol and the toluene.
Template magnesium oxide can use the magnesium oxide of different specific surface areas.The magnesium oxide of high-specific surface area means less magnesium oxide particle diameter, is suitable as the template of small-bore mesoporous carbon; The magnesium oxide of low specific surface area means larger magnesium oxide particle diameter, is suitable as the template of wide aperture mesoporous carbon.The common general specific surface area of reagent oxidation magnesium is lower, and size distribution is wider, but cheap and easy to get, still can be used as the template that the present invention prepares the high-performance Mesoporous Carbon Materials.To the Mesoporous Carbon Materials of particular requirement is arranged, can select the special nano magnesia commodity that are fit to, or the self-control using magnesium oxide template uses.The specific surface area scope of the using magnesium oxide template that the present invention uses can be 10m 2/ g-1000m 2/ g, preferred 20-600m 2/ g specifically can be 20-428m 2/ g, 36-401m 2/ g, 39-369m 2/ g, 47-228m 2/ g or 20-196m 2/ g.
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 10m 2/ g-30m 2The amount ratio of the described using magnesium oxide template of/g is 0.4g-900g: 1g-80g: 100g, and preferred 0.6g-50g: 1.5g-27g: 100g specifically can be 0.085: 0.05: 1;
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 31m 2/ g-100m 2The amount ratio of the described using magnesium oxide template of/g is 0.8g-900g: 2g-110g: 100g, preferred 1.3g-80g: 3g-45g: 100g specifically can be 0.04-6: 0.07-0.2: 1,0.05-0.17: 0.07-0.2: 1,0.08-0.15: 0.07-0.2: 1,0.09-0.1: 0.07-0.2: 1,0.04-6: 0.09-0.2: 1,0.05-0.17: 0.09-0.2: 1,0.08-0.15: 0.09-0.2: 1,0.09-0.1: 0.09-0.2: 1,0.04-6: 0.1-0.2: 1,0.05-0.17: 0.1-2: 1,0.08-0.15: 0.1-0.2: 1,0.09-0.1: 0.1-0.2: 1;
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 101m 2/ g-300m 2The amount ratio of the described using magnesium oxide template of/g is 1.5g-900g; 4g-140g: 100g, preferred 3g-100g: 7g-65g: 100g specifically can be 0.17-7: 0.12-0.25: 1,0.5-4.6: 0.12-0.25: 1,0.17-7: 0.12-0.2: 1,0.5-4.6: 0.12-0.2: 1;
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 301m 2/ g-1000m 2The amount ratio of the using magnesium oxide template of/g is 4g-900g: 10g-180g: 100g, preferred 7g-180g: 15g-110g: 100g specifically can be 0.2-0.8: 0.3-0.6: 1,0.3-0.5: 0.3-0.6: 1,0.4-0.8: 0.3-0.6: 1.
In the described polymerization procedure, temperature is 30-180 ℃, and preferred 80-120 ℃, more preferably 90 ℃, the time is 1-72 hour, preferred 3-6 hour.
Described inert atmosphere all is selected from least a in nitrogen atmosphere, helium atmosphere and the argon gas atmosphere, preferred nitrogen or argon gas atmosphere; Described temperature rise rate is 1-50 ℃/min by in the room temperature heating step, preferred 5-10 ℃/min; In the described charing step, temperature is 600-1500 ℃, specifically can be 600-1100 ℃, 600-1000 ℃, 600-900 ℃, 600-800 ℃, 800-1100 ℃, 800-1000 ℃, 800-900 ℃, 900-1100 ℃, 900-1000 ℃ or 1000-1100 ℃, preferred 700-1200 ℃, time is 1 minute to 24 hours, specifically can be 0.5 hour-3 hours, 1 hour-3 hours or 0.5 hour-1 hour, preferred 1 hour-6 hours.
Described acid can be any can dissolved oxygen magnesium and do not produce acid compounds or its mixture of new insoluble solid matter.As being selected from least a in mineral acid and the organic acid; Wherein, described mineral acid all is selected from least a in hydrochloric acid, sulfuric acid and the nitric acid, and described organic acid all is selected from least a in acetic acid, citric acid and the ethylenediamine tetraacetic acid (EDTA).The consumption of acid all can to excessive greatly to magnesian amount is slightly excessive.Stirring and heating can be accelerated the speed of magnesium oxide dissolving.Treat the magnesium oxide dissolve complete, can filter, centrifugal or decant carries out solid-liquid separation.With pure water to solid product washing for several times, to the solid product the content of the impurity such as magnesium ion till meet the requirements.Used pure water can be deionized water, distilled water etc., if will go not highly to the foreign matter content of final product, also can use tap water etc.Solid product through washing needs drying usually, and its moisture content is met the requirements.Heating, air blast or the method that vacuumizes can improve dry efficient.
The Mesoporous Carbon Materials for preparing according to the method described above and the application of this Mesoporous Carbon Materials in Kaolinite Preparation of Catalyst, sorbing material or electrode materials also belong to protection scope of the present invention.
The mesoporous carbon for preparing according to the method described above also belongs to protection scope of the present invention.The method for preparing Mesoporous Carbon Materials provided by the invention is a kind of pervasive method for preparing Mesoporous Carbon Materials.The Mesoporous Carbon Materials of (2nm-50nm) any aperture and any pore structure in the mesopore scope theoretically, can by the using magnesium oxide template of selecting to be fit to, be used method of the present invention and be synthesized into.
The Mesoporous Carbon Materials that the invention described above provides, its BET specific surface area is 1014-2618m 2/ g, nitrogen absorption total hole volume 2.2-5.8cm 3/ g, t-figure method microporosity is less than 4%, and mean pore size is 3.7-18nm, and the most probable aperture is 3.3-43nm.
It is raw material that the present invention adopts micromolecular phenolic compound and aldehyde compound, method by the surface catalysis polymerization, the even coated magnesium oxide of resin that obtains, at first aggregate into superpolymer with small molecules, being mixed to get the carbon precursor coated magnesium oxide with magnesium oxide by powder mixing or solution again compares, not only shorten flow process, reduced cost, the more important thing is the homogeneity and the Modulatory character that have greatly strengthened the carbon precursor coating layer.The characteristics of superpolymer are that molecular weight is huge, also be bulky at molecular scale therefore, and generally molecular weight have a distribution, is not complete and homogeneous.Huge molecular volume must hinder high-polymer molecular to the uniform fold of template internal pore surface.All the more so to small-bore mesopore hole, can only reach the effect of a filling in a lot of situations.Through carbonization process, volumetric shrinkage, acquisition will be the product of heavy wall, and thicker mesopore hole wall also produces many micropores easily in the process of volumetric shrinkage.If deliberately adopt the superpolymer of molecular weight and the carbon precursor consumption less with respect to template, because between the high-polymer molecular general lack effective key and, after the char volume contraction, may cause discontinuous and imperfect at template surface of the charcoal layer that forms, caving in of charcoal skeleton can occur after removing template, obtain specific surface area and pore volume diminishes, the product that mesoporous is low.
Method of the present invention is to allow micromolecular compound evenly spread to the surface of template, even the mesopore hole of small-bore has at first had the advantage of dispersion aspect.Then, utilize magnesian alkalescence by small molecules at template surface, catalysis forms polymkeric substance, has guaranteed the fully applying of polymer layer and template surface, has given full play to the advantage that hard template method can accurately be controlled by template product porous charcoal pore structure.Consumption and polymerizing condition by strict control resol precursor, can form on the using magnesium oxide template surface macromolecule layer of a kind of even two-dimensional network structure or accurate two-dirnentional structure, through high temperature carbonization, obtain even thickness less than the charcoal layer capping oxidation magnesium of 1 nanometer than continuous whole, removing template is exactly the high mesoporous thin-walled of the high pore volume of high-specific surface area Mesoporous Carbon Materials, and this is the advantage of thin-walled.If improve the consumption of resol precursor, the even two-dimensional network structure that forms on the using magnesium oxide template surface can be to the macromolecule layer development of three-dimensional continuous structure uniform thickness, through high temperature carbonization, what obtain is the charcoal layer capping oxidation magnesium of even thickness nano level continuous whole, remove the heavy wall Mesoporous Carbon Materials that template obtains being regulated and control by resol precursor consumption pore wall thickness, this is the advantage that hole wall can evenly be regulated and control.
The present invention designs ingenious, and raw material is cheap and easy to get, and technological process is simply green, and product performance are remarkable, towards high-end applications.Mesoporous Carbon Materials provided by the invention is keeping mesoporous to surpass in 95% the situation, and high-specific surface area can surpass 2600m 2/ g, maximum mesopore volume can surpass 5.5cm 3/ g.Method provided by the invention at aspects such as the pore size distribution of regulating and control Mesoporous Carbon Materials and pore wall thicknesses, has the clear superiority that present known existing technologies can't be equal to, and is worth wideling popularize application in fields such as catalysis, absorption, electrode materialss.
Description of drawings
Fig. 1 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 1 preparation gained mesoporous carbon.
Fig. 2 is the feature transmission electron microscope photo of embodiment 1 preparation gained mesoporous carbon.
Fig. 3 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 5 preparation gained mesoporous carbons.
Fig. 4 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 6 preparation gained mesoporous carbons.
Fig. 5 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 7 preparation gained mesoporous carbons.
Fig. 6 is the feature transmission electron microscope photo of embodiment 7 preparation gained mesoporous carbons.
Fig. 7 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 8 preparation gained mesoporous carbons.
Fig. 8 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 9 preparation gained mesoporous carbons.
Fig. 9 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 10 preparation gained mesoporous carbons.
Figure 10 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 11 preparation gained mesoporous carbons.
Figure 11 is the feature transmission electron microscope photo of embodiment 11 preparation gained mesoporous carbons.
Figure 12 is the feature transmission electron microscope photo of embodiment 12 preparation gained mesoporous carbons.
Figure 13 is the feature transmission electron microscope photo of embodiment 13 preparation gained mesoporous carbons.
Figure 14 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 14 preparation gained mesoporous carbons.
Figure 15 is the feature transmission electron microscope photo of embodiment 14 preparation gained mesoporous carbons.
Figure 16 is the feature transmission electron microscope photo of embodiment 15 preparation gained mesoporous carbons.
Figure 17 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 16 preparation gained mesoporous carbons.
Figure 18 is the feature transmission electron microscope photo of embodiment 16 preparation gained mesoporous carbons.
Figure 19 is the feature transmission electron microscope photo of embodiment 17 preparation gained mesoporous carbons.
Figure 20 is the feature nitrogen absorption under low temperature pore size distribution curve of embodiment 21 preparation gained mesoporous carbons.
Figure 21 is the feature transmission electron microscope photo of embodiment 21 preparation gained mesoporous carbons.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.
For the different application of porous carbon material, high performance index request can be different.For example for the application of absorption aspect, high-specific surface area is a basic index, and the super-activated carbon of superhigh specific surface area has the performance higher than common absorbent charcoal material.For the adsorbate of selecting absorption specific molecular size, only have the aperture of sorbent material and the size that is adsorbed molecule or ion to be complementary, could obtain maximum loading capacity.The application of Mesoporous Carbon Materials, more be for nanoscale than macromole or ion, at catalytic field, also can relate to some nanoparticle.In this case, the internal surface in smaller aperture due space or become unreachable surface or difficult accessible surface, also can only be considered to invalid specific surface area corresponding to this part surperficial specific surface area, and accessible surface or specific surface area easy and that the surface is corresponding could be claimed think effective ratio area.For Mesoporous Carbon Materials, high effective ratio area is to high performance further index request.The index of microporosity has reflected the height of the invalid specific surface area of Mesoporous Carbon Materials to a certain extent in conjunction with the index of specific surface area, because the mesopore of majority is used, micropore specific area can roughly all belong within the scope of invalid specific surface area.In addition, to certain the concrete application of high-performance Mesoporous Carbon Materials, specific pore structure or pore size distribution also are a special index to a great extent.
Embodiment 1
1) with nano oxidized magnesium dust (specific surface area 369m 2/ g) 4.6g, Resorcinol 1.4g, furfural 1.7g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 50mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 1mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water, and oven dry obtains mesoporous carbon provided by the invention.
The BET specific surface area 2618m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.7cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 4.2nm, most probable aperture 3.7nm.Fig. 1 and Fig. 2 are respectively this embodiment and prepare the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon and the feature transmission electron microscope photo of mesoporous carbon.The pore size distribution of this mesoporous carbon is more concentrated as can be seen from Figure 1; As shown in Figure 2, this material possesses the feature of mesopore thin-walled.
Embodiment 2:
1) with nano oxidized magnesium dust (specific surface area 401m 2/ g) 5.2g, Resorcinol 3.0g, mass percentage concentration is 37% formalin 3.2g, carries out polyreaction 3 hours in 90 ℃ behind the ethanol 45mL mixing, reacts the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1975m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.4cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 4.8nm, most probable aperture 3.4nm.
Embodiment 3:
1) with nano oxidized magnesium dust (specific surface area 401m 2/ g) 5.2g, Resorcinol 3.0g, phenyl aldehyde 4.2g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 50mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 1mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1782m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 1.6cm 3/ g, t-figure method microporosity be less than 5%, mean pore size 3.7nm, most probable aperture 3.6nm.
Embodiment 4:
1) with nano oxidized magnesium dust (specific surface area 401m 2/ g) 5.0g, Resorcinol 3.0g, Paraformaldehyde 96 (analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group, production code member 80096692) 1.7g, carried out polyreaction 3 hours in 90 ℃ behind the ethanol 50mL mixing, react the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 1mol/L nitric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1997m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.4cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 4.8nm, most probable aperture 3.3nm.
Embodiment 5:
1) with nano oxidized magnesium dust (specific surface area 428m 2/ g) 10.2g, Resorcinol 3.2g, furfural 4.6g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 60mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 900 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 1mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 2175m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.6cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 4.7nm, most probable aperture 3.7nm.Fig. 3 prepares the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon for this embodiment.As shown in Figure 3, the pore size distribution of this mesoporous carbon is more concentrated.
Embodiment 6:
According to embodiment 5 identical steps, only with step 2) carbonization temperature and time replaces with: 1000 ℃ of charings 3 hours obtain mesoporous carbon.
The BET specific surface area 2451m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 3.2cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 5.2nm, most probable aperture 3.7nm.Fig. 4 prepares the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon for this embodiment.As shown in Figure 4, the pore size distribution of this mesoporous carbon is more concentrated.
Embodiment 7:
According to embodiment 5 identical steps, only with step 2) carbonization temperature and time replaces with: 1100 ℃ of charings 3 hours obtain mesoporous carbon.
The BET specific surface area 2361m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 3.5cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 5.9nm, most probable aperture 4.0nm.Fig. 5 and Fig. 6 are respectively this embodiment and prepare the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon and the feature transmission electron microscope photo of mesoporous carbon.As shown in Figure 5, the pore size distribution of this mesoporous carbon is more concentrated; As shown in Figure 6, this material possesses the feature of mesopore thin-walled.
Embodiment 8:
1) with nano oxidized magnesium dust (specific surface area 228m 2/ g) 6.8g, Resorcinol 1.5g, furfural 3.5g carried out polyreaction 3 hours in 90 ℃ behind the propyl carbinol 40mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 1 hour by room temperature with the temperature rise rate of 10 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1964m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.7cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 5.5nm, most probable aperture 4.1nm.Fig. 7 prepares the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon for this embodiment.As shown in Figure 7, the pore size distribution of this mesoporous carbon is more concentrated.
Embodiment 9:
1) with nano oxidized magnesium dust (specific surface area 195m 2/ g) 1.0g, Resorcinol 0.20g, furfural 4.6g carried out polyreaction 3 hours in 90 ℃ behind the mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 900 ℃ of charings 1 hour by room temperature with the temperature rise rate of 10 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 4mol/L acetic acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1780m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.9cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 6.4nm, most probable aperture 4.4nm.Fig. 8 prepares the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon for this embodiment.As shown in Figure 8, the pore size distribution of this mesoporous carbon is more concentrated.
Embodiment 10:
1) with nano oxidized magnesium dust (specific surface area 195m 2/ g) 1.0g, Resorcinol 0.25g carried out polyreaction 3 hours in 90 ℃ behind the furfural 7.0g mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 1 hour by room temperature with the temperature rise rate of 10 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 2066m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 3.3cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 6.3nm, most probable aperture 4.9nm.Fig. 9 prepares the feature nitrogen absorption under low temperature pore size distribution curve of gained mesoporous carbon for this embodiment.As shown in Figure 9, the pore size distribution of this mesoporous carbon is more concentrated.
Embodiment 11:
1) with nano oxidized magnesium dust (specific surface area 196m 2/ g) 10.0g, phenol 1.2g, furfural 1.7g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 100mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 2561m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.9cm 3/ g, t-figure method microporosity be less than 1%, mean pore size 4.5nm, most probable aperture 4.1nm.Figure 10 and Figure 11 are respectively feature nitrogen absorption under low temperature pore size distribution curve and the feature transmission electron microscope photo that this embodiment prepares the gained mesoporous carbon.As shown in Figure 10, the pore size distribution of this mesoporous carbon is more concentrated; As shown in Figure 11, this material possesses the feature of mesopore thin-walled.
Embodiment 12:
1) with nano oxidized magnesium dust (specific surface area 47m 2/ g) 2.0g, Resorcinol 0.20g, furfural 12g carried out polyreaction 3 hours in 90 ℃ behind the mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 1 hour by room temperature with the temperature rise rate of 10 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L acetic acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1304m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.9cm 3/ g, t-figure method microporosity be less than 4%, mean pore size 8.9nm, most probable aperture 20nm.Figure 12 prepares the feature transmission electron microscope photo of gained mesoporous carbon for this embodiment.As shown in Figure 12, this material possesses the feature of mesopore thin-walled.
Embodiment 13:
1) with nano oxidized magnesium dust (specific surface area 47m 2/ g) 5.6g, Resorcinol 0.29g, furfural 21g carried out polyreaction 3 hours in 90 ℃ behind the mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 1 hour by room temperature with the temperature rise rate of 10 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1519m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.5cm 3/ g, t-figure method microporosity be less than 4%, mean pore size 6.6nm, most probable aperture 17nm.Figure 13 prepares the feature transmission electron microscope photo of gained mesoporous carbon for this embodiment.As shown in Figure 13, this material possesses the feature of mesopore thin-walled.
Embodiment 14:
1) with embodiment 13 steps 2) the magnesium oxide 2.5g that coats of gained charcoal, Resorcinol 0.13g, furfural 14g carried out polyreaction 3 hours in 90 ℃ behind the mixing, react the complete magnesium oxide that obtains the coating of resin secondary, again with its oven dry;
2) in inert atmosphere, the magnesium oxide that gained resin secondary is coated is warming up to 800 ℃ of charings 1 hour by room temperature with the temperature rise rate of 10 ℃/min, obtains the magnesium oxide that the charcoal secondary coats;
3) magnesium oxide that gained charcoal secondary is coated is removed using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1376m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 4.5cm 3/ g, t-figure method microporosity be less than 3%, mean pore size 13nm, most probable aperture 17nm.Figure 14 and Figure 15 are respectively feature nitrogen absorption under low temperature pore size distribution curve and the feature transmission electron microscope photo that this embodiment prepares the gained mesoporous carbon.As shown in Figure 14, the pore size distribution of this mesoporous carbon is more concentrated; As shown in Figure 15, this material possesses the feature of mesopore thin-walled.
Embodiment 15:
1) with nano oxidized magnesium dust (specific surface area 36m 2/ g) 20g, Resorcinol 1.4g, furfural 2.3g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 80mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 2081m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 5.4cm 3/ g, t-figure method microporosity be less than 2%, mean pore size 10nm, most probable aperture 25nm.Figure 16 prepares the feature transmission electron microscope photo of gained mesoporous carbon for this embodiment.As shown in Figure 16, this material possesses the feature of mesopore thin-walled.
Embodiment 16:
1) with nano oxidized magnesium dust (specific surface area 36m 2/ g) 20g, Resorcinol 1.8g, furfural 2.9g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 80mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1724m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 5.8cm 3/ g, t-figure method microporosity be less than 3%, mean pore size 13nm, most probable aperture 25nm.Figure 17 and Figure 18 are respectively feature nitrogen absorption under low temperature pore size distribution curve and the feature transmission electron microscope photo that this embodiment prepares the gained mesoporous carbon.As shown in Figure 17, the pore size distribution of this mesoporous carbon is more concentrated; As shown in Figure 18, this material possesses the feature of mesopore thin-walled.
Embodiment 17:
1) with reagent light magnesium oxide (analytical pure) powder (specific surface area 39m 2/ g) 5g, Resorcinol 1.0g, Paraformaldehyde 96 (analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group, production code member 80096692) 0.5g, carried out polyreaction 3 hours in 90 ℃ behind the ethanol 50mL mixing, react the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 0.5 hour by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 1mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1595m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 3.8cm 3/ g, t-figure method microporosity be less than 2%, mean pore size 9.5nm, most probable aperture 14nm.Figure 19 prepares the feature transmission electron microscope photo of gained mesoporous carbon for this embodiment.As shown in Figure 19, this material possesses the feature of mesopore thin-walled.
Embodiment 18:
1) with reagent light magnesium oxide (analytical pure) powder (specific surface area 39m 2/ g) 20g, Resorcinol 4.0g, Paraformaldehyde 96 (analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group, production code member 80096692) 1.6g, carried out polyreaction 3 hours in 90 ℃ behind the ethanol 150mL mixing, react the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 600 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1014m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.2cm 3/ g, t-figure method microporosity be less than 5%, mean pore size 8.8nm, most probable aperture 25nm.
Embodiment 19:
According to embodiment 18 identical steps, only with step 2) carbonization temperature and time replaces with: 800 ℃ of charings 3 hours obtain mesoporous carbon.
The BET specific surface area 1338m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 3.1cm 3/ g, t-figure method microporosity be less than 4%, mean pore size 9.2nm, most probable aperture 25nm.
Embodiment 20:
1) with reagent light magnesium oxide (analytical pure) powder (specific surface area 39m 2/ g) 20g, phenol 4.1g, Paraformaldehyde 96 (analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group, production code member 80096692) 1.8g, carried out polyreaction 6 hours in 90 ℃ behind the toluene 40mL mixing, react the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1426m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 3.3cm 3/ g, t-figure method microporosity be less than 3%, mean pore size 9.4nm, most probable aperture 13nm.
Embodiment 21:
According to embodiment 20 identical steps, only with step 2) carbonization temperature and time replaces with: 1000 ℃ of charings 3 hours obtain mesoporous carbon.
The BET specific surface area 1523m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 4.8cm 3/ g, t-figure method microporosity be less than 3%, mean pore size 13nm, most probable aperture 15nm.Figure 20 and Figure 21 are respectively feature nitrogen absorption under low temperature pore size distribution curve and the feature transmission electron microscope photo that this embodiment prepares the gained mesoporous carbon.As shown in Figure 20, the pore size distribution of this mesoporous carbon is wider; As shown in Figure 21, this material possesses the feature of mesopore thin-walled.
Embodiment 22:
1) with reagent light magnesium oxide (analytical pure) powder (specific surface area 39m 2/ g) 20g, Resorcinol 2.0g, mass percentage concentration is 37% formalin 2.2g, carries out polyreaction 3 hours in 90 ℃ behind the ethanol 50mL mixing, reacts the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 900 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1269m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 2.6cm 3/ g, t-figure method microporosity be less than 4%, mean pore size 8.2nm, most probable aperture 25nm.
Embodiment 23:
1) with reagent light magnesium oxide (analytical pure) powder (specific surface area 39m 2/ g) 20g, Resorcinol 2.0g, mass percentage concentration is 37% formalin 2.7g, carries out polyreaction 3 hours in 90 ℃ behind the ethanol 50mL mixing, reacts the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 800 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 2mol/L hydrochloric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1390m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 5.4cm 3/ g, t-figure method microporosity be less than 2%, mean pore size 16nm, most probable aperture 23nm.
Embodiment 24:
1) with nano oxidized magnesium dust (specific surface area 20m 2/ g) 20g, Resorcinol 1.0g, furfural 1.7g carried out polyreaction 3 hours in 90 ℃ behind the ethanol 70mL mixing, reacted the complete magnesium oxide that obtains resin-coated, again with its oven dry;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated is warming up to 1000 ℃ of charings 3 hours by room temperature with the temperature rise rate of 5 ℃/min, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal removes using magnesium oxide template with 1mol/L sulfuric acid, filters, and solid product is washed till neutrality with deionized water.Oven dry obtains mesoporous carbon.
The BET specific surface area 1232m of this mesoporous carbon 2/ g, nitrogen absorption total hole volume 5.4cm 3/ g, t-figure method microporosity be less than 4%, mean pore size 18nm, most probable aperture 43nm.

Claims (10)

1. a method for preparing Mesoporous Carbon Materials comprises the steps:
1) liquid aldehyde compounds, phenolic compound and using magnesium oxide template mixing are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
Perhaps, solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and using magnesium oxide template mixing in solvent are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated carries out charing after being heated up by room temperature, obtains the magnesium oxide that charcoal coats;
3) with described step 2) magnesium oxide that coats of gained charcoal dissolves magnesium oxide with sour mixing, obtains described Mesoporous Carbon Materials.
2. a method for preparing Mesoporous Carbon Materials comprises the steps:
1) liquid aldehyde compounds, phenolic compound and using magnesium oxide template mixing are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
Perhaps, solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and using magnesium oxide template mixing in solvent are carried out polyreaction, react the complete magnesium oxide that obtains resin-coated;
2) in inert atmosphere, with described step 1) magnesium oxide of gained resin-coated carries out charing after being heated up by room temperature, obtains the magnesium oxide that charcoal coats;
3) with described step 2) gained the charcoal magnesium oxide, described liquid aldehyde compounds and the described phenolic compound mixing that coat carry out described polyreaction, react the complete magnesium oxide that obtains the coating of resin secondary;
Perhaps, with described step 2) gained the charcoal magnesium oxide, described solid aldehyde compounds or the described liquid aldehyde compounds that coat or gaseous aldehyde compounds and described phenolic compound mixing in described solvent carry out polyreaction, react the complete magnesium oxide that obtains the coating of resin secondary;
4) in inert atmosphere, with described step 3) magnesium oxide that coats of gained resin secondary carries out charing after being heated up by room temperature, obtains the magnesium oxide that the charcoal secondary coats;
5) with described step 4) magnesium oxide that coats of gained charcoal secondary dissolves magnesium oxide with sour mixing, obtains described Mesoporous Carbon Materials.
3. method according to claim 1 and 2, it is characterized in that: described liquid aldehyde compounds all is selected from least a in acetaldehyde, propionic aldehyde, butyraldehyde, hexanal, propenal, crotonic aldehyde, furfural, phenyl aldehyde, phenylacetic aldehyde, phenylacrolein, salicylic aldehyde, oxalic dialdehyde and the paraldehyde, at least a in preferred furfural and the phenyl aldehyde;
Described solid aldehyde compounds all is selected from least a in trioxymethylene, Paraformaldehyde 96, terephthal aldehyde and the Vanillin, at least a in preferred trioxymethylene and the Paraformaldehyde 96;
Described gaseous aldehyde compounds all is selected from least a in formaldehyde and the acetaldehyde, preferred formaldehyde;
Described phenolic compound all is selected from least a in phenol, dihydroxy-benzene, benzenetriol, cresols, xylenol, tert.-butyl phenol, chavicol, thymol, methoxyl group phenol, naphthols and the cardanol, at least a in preferred phenol, dihydroxy-benzene and the cresols;
Described solvent all is selected from least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, n-hexyl alcohol, hexalin, ethylene glycol, propylene glycol, ether, tetrahydrofuran (THF), acetone, butanone, furfural, benzene,toluene,xylene, trimethylbenzene, ethylbenzene and the dimethyl sulfoxide (DMSO), at least a in preferred alcohol, the trimethyl carbinol and the toluene;
The specific surface area of described using magnesium oxide template is 10m 2/ g-1000m 2/ g, preferred 20-600m 2/ g.
4. arbitrary described method according to claim 1-3 is characterized in that: described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 10m 2/ g-30m 2The amount ratio of the described using magnesium oxide template of/g is 0.4g-900g: 1g-80g: 100g, preferred 0.6g-50g: 1.5g-27g: 100g;
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 31m 2/ g-100m 2The amount ratio of the described using magnesium oxide template of/g is 0.8g-900g: 2g-110g: 100g, preferred 1.3g-80g: 3g-45g: 100g;
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 101m 2/ g-300m 2The amount ratio of the described using magnesium oxide template of/g is 1.5g-900g: 4g-140g: 100g, preferred 3g-100g: 7g-65g: 100g;
Described solid aldehyde compounds or described liquid aldehyde compounds or gaseous aldehyde compounds, phenolic compound and specific surface area are 301m 2/ g-1000m 2The amount ratio of the using magnesium oxide template of/g is 4g-900g: 10g-180g: 100g, preferred 7g-180g: 15g-110g: 100g.
5. arbitrary described method according to claim 1-4 is characterized in that: described acid all is selected from least a in mineral acid and the organic acid; Wherein, described mineral acid all is selected from least a in hydrochloric acid, sulfuric acid and the nitric acid, and described organic acid all is selected from least a in acetic acid, citric acid and the ethylenediamine tetraacetic acid (EDTA).
6. arbitrary described method according to claim 1-5, it is characterized in that: in the described polymerization procedure, temperature is 30-180 ℃, and preferred 80-120 ℃, more preferably 90 ℃, the time is 1-72 hour, preferred 3-6 hour.
7. arbitrary described method according to claim 1-6 is characterized in that: described inert atmosphere all is selected from least a in nitrogen atmosphere, helium atmosphere and the argon gas atmosphere, preferred nitrogen or argon gas atmosphere; Described temperature rise rate is 1-50 ℃/min by in the room temperature heating step, preferred 5-10 ℃/min; In the described charing step, temperature is 600-1500 ℃, and preferred 700-1200 ℃, the time is 1 minute to 24 hours, preferred 1 hour-6 hours.
8. the Mesoporous Carbon Materials for preparing of the arbitrary described method of claim 1-7.
9. Mesoporous Carbon Materials according to claim 8, it is characterized in that: the BET specific surface area of described Mesoporous Carbon Materials is 1014-2618m 2/ g, nitrogen absorption total hole volume 2.2-5.8cm 3/ g, t-figure method microporosity is less than 4%, and mean pore size is 3.7-18nm, and the most probable aperture is 3.3-43nm.
10. claim 8 or the application of 9 described Mesoporous Carbon Materials in Kaolinite Preparation of Catalyst, sorbing material, electrode materials or biological medicine material.
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CN110523374A (en) * 2019-08-09 2019-12-03 华南理工大学 A kind of adsorbing separation CH4/N2、C2H6/CH4Rice base granular carbon material and the preparation method and application thereof
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CN113332984A (en) * 2021-05-20 2021-09-03 济南大学 Preparation method and application of cobalt-carbon catalyst prepared by polymerization reaction
CN115215337A (en) * 2022-05-24 2022-10-21 中国科学院兰州化学物理研究所 Method for synthesizing phenolic resin and preparing carbon material

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CN103466598A (en) * 2013-09-13 2013-12-25 中盈长江国际新能源投资有限公司 Method for preparing nitrogen-containing ordered mesoporous carbon (OMC) materials based on biomass bases
CN106082165A (en) * 2016-06-12 2016-11-09 太原理工大学 The preparation method of micro-composite mesoporous material with carbon element
CN106082165B (en) * 2016-06-12 2018-06-01 太原理工大学 The preparation method of micro- composite mesoporous carbon material
CN106495127A (en) * 2016-11-15 2017-03-15 河南理工大学 A kind of simple method for preparing of mesoporous carbon
CN107188171B (en) * 2017-06-21 2019-05-28 武汉工程大学 Porous carbon materials and preparation method and the porous carbon-based electrode material for supercapacitor prepared using the porous carbon materials
CN107188171A (en) * 2017-06-21 2017-09-22 武汉工程大学 Porous carbon materials and its preparation method and the porous carbon-based electrode material for ultracapacitor prepared using the porous carbon materials
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CN109201046A (en) * 2018-09-06 2019-01-15 青岛科技大学 A kind of preparation method and applications of the residual tar base mesoporous carbon supported noble metal catalyst of kettle
CN109174073A (en) * 2018-09-06 2019-01-11 青岛科技大学 The resource utilization method of the residual tar of kettle in a kind of production of phenylenediamine
CN109174073B (en) * 2018-09-06 2021-04-06 青岛科技大学 Resource utilization method of still residual tar in phenylenediamine production
CN109494082A (en) * 2018-11-19 2019-03-19 中物院成都科学技术发展中心 A kind of N doping porous graphite alkenes carbon nanosheet material and its preparation method and application
CN109850871B (en) * 2019-01-28 2022-06-28 安徽大学 Nitrogen-doped porous carbon nanosheet and preparation method thereof
CN109850871A (en) * 2019-01-28 2019-06-07 安徽大学 A kind of porous carbon nanosheet of N doping and preparation method thereof
CN110127692A (en) * 2019-05-24 2019-08-16 许皖 A kind of preparation method of mesoporous heat-resistant activity charcoal
CN110523374A (en) * 2019-08-09 2019-12-03 华南理工大学 A kind of adsorbing separation CH4/N2、C2H6/CH4Rice base granular carbon material and the preparation method and application thereof
CN110523374B (en) * 2019-08-09 2022-12-16 华南理工大学 Adsorption separation CH 4 /N 2 、C 2 H 6 /CH 4 Rice-based granular carbon material and preparation method and application thereof
CN110813241A (en) * 2019-12-17 2020-02-21 国网山东综合能源服务有限公司 Nitrogen-oxygen co-doped porous carbon material and preparation method and application thereof
CN112167706A (en) * 2020-09-28 2021-01-05 江苏中烟工业有限责任公司 Additive for cigarette filter stick for reducing ammonia in cigarette smoke and application thereof
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