CN104888708A - Corn bran-based three-dimensional multi-level pore structure carbon material and preparation method thereof - Google Patents
Corn bran-based three-dimensional multi-level pore structure carbon material and preparation method thereof Download PDFInfo
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- CN104888708A CN104888708A CN201510381791.1A CN201510381791A CN104888708A CN 104888708 A CN104888708 A CN 104888708A CN 201510381791 A CN201510381791 A CN 201510381791A CN 104888708 A CN104888708 A CN 104888708A
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Abstract
The invention relates to a corn bran-based three-dimensional multi-level pore structure carbon material and a preparation method thereof, which belong to three-dimensional multi-level pore structure carbon materials. According to the corn bran-based three-dimensional multi-level pore structure carbon material and the preparation method, renewable biomass corn bran with low price and rich yield is adopted as a carbon source, the novel three-dimensional multi-level pore structure carbon material is effectively prepared by adopting a simple template-free method which is easy to industrialize, and the problems of process complexity, time consumption, high cost and difficulty in realizing industrialization of a template method are solved. The corn bran-based three-dimensional multi-level pore structure carbon material is prepared in the following steps of cutting the corn bran into pieces, drying after water washing treatment, then adding to a KOH solution, returning under a water bath condition, sieving after cooling, then roasting solids in high-purity nitrogen atmosphere, then cleaning with a hydrochloric acid solution, centrifuging, washing with water and drying. The specific surface area of the carbon material reaches up to 927m<2>g-1, macropore, mesopore and micropore structures are mutually communicated, the pore size distribution is centered, an oxygen enrichment functional group is contained, and the content is 12% to 17%.
Description
Technical field
The invention belongs to three-dimensional multistage pore structure material with carbon element; Be specifically related to corn scytoblastema three-dimensional multistage pore structure material with carbon element and preparation method thereof.
Background technology
Three-dimensional multistage hole carbon (3D-HPCs) causes extensive researcher as the electrode carbon material of a class novelty and sorbing material and payes attention to and pay close attention to.3D-HPCs has unique pore structure and topological structure, shows many advantages, comprising: the macropore that (1) is interconnected, mesoporous and micropore pore structure in above-mentioned application; (2) high-ratio surface; (3) continuous print electron transmission path; (4) pore-size distribution is narrow.Wherein, the hierarchical porous structure interconnected is of value to the quick transmission of ion, and high-specific surface area can provide wide active interface, has superior chemical property and absorption property.
At present, the preparation method of three-dimensional multistage hole carbon mainly adopts hard template method and soft template method, there is Template preparation and the shortcoming such as removing process complexity is loaded down with trivial details, consuming time, secondary pollution environment for die version method; And for soft template method, there is the problems such as template is expensive, carbon source requires harsh and generated time long.The above-mentioned defect of these two kinds of methods, causes the cost performance of prepared multi-stage porous carbon material very low, hinders industrialized application to a certain extent.Therefore, explore a kind of method without template synthesis multi-stage porous carbon of simple, environmental protection, particularly adopt continuable living beings as low price carbon source, have important practical significance, especially a challenging job.
Maize peel, as a kind of corn planting accessory substance of abundance, produces 1450 × 10 in China every year
4the maize peel of ton, can be used as the multi-stage porous carbon material that cheap living beings carbon source preparation is advanced.If successfully explore the three-dimensional multistage pore structure material with carbon element of maize peel as carbon source preparation advanced person, by promoting the commercial applications of three-dimensional multistage hole material with carbon element, bring considerable value and economic benefit to agricultural.
At present, most of maize peel is all lost as agricultural wastes or is burnt, and not only wastes resource but also contaminated environment.So, need the Method and process of the efficiency utilization exploring maize peel badly, make full use of this renewable biomass resource.Up to the present, method that is simple, that be easy to industrial applications is adopted to prepare the unmanned report of three-dimensional multistage hole carbon by maize peel.
Summary of the invention
The object of the invention there is provided a kind of three-dimensional multistage hole material with carbon element utilizing maize peel to prepare and preparation method thereof.The present invention adopts cheap, abundance, renewable biomass maize peel as carbon source, by simple, be easy to industrialized and effectively prepare three-dimensional multistage pore structure new carbon without template, solve that template process is loaded down with trivial details, consuming time, cost is high, be difficult to realize an industrialized difficult problem.
In the present invention, corn scytoblastema three-dimensional multistage pore structure material with carbon element is successively through shredding, washing process post-drying by maize peel, then add in KOH solution, reflux under water bath condition again, sieve after cooling, then by solid roasting under high pure nitrogen atmosphere, then successively through hydrochloric acid solution cleaning, centrifugal, washing and drying and processing.
In the present invention, the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element carries out in the steps below:
Step one, maize peel to be shredded, dry under 100 DEG C of conditions after washing;
Step 2, be that the maize peel processed through step one is added mass concentration is in the KOH solution of 2% ~ 10% to 1 ﹕ (10 ~ 20) proportioning by the mass ratio of maize peel and KOH solution, then reflux 2h ~ 6h (obtaining brown colloidal liquid) in 60 DEG C ~ 120 DEG C water-baths, with 200 order stainless steel screen filtration after cooling, leave solid;
Step 3, solid step 2 obtained are dried and are placed in quartz tube furnace, roasting 1 ~ 2h (gray solid) under high pure nitrogen (volume fraction is purity is 99.999%) atmosphere, temperature are 600 ~ 1000 DEG C of conditions;
Step 4 is then with hydrochloric acid solution cleaning (object removes sylvite), centrifugal, washed several times with water post-drying; Namely corn scytoblastema three-dimensional multistage pore structure material with carbon element is obtained.
The present invention is in the building-up process of multi-stage porous corn scytoblastema material with carbon element, and KOH plays multiple action: the cellulose in maize peel and hemicellulose/lignin, as pretreating agent, are effectively separated by (1) KOH; (2) remaining in cellulose KOH crystallite plays the effect manufacturing macropore; (3) KOH makes a large amount of micropore as activator, improves the specific area of material with carbon element.
Corn scytoblastema three-dimensional multistage hole of the present invention material with carbon element has the physicochemical properties of many uniquenesses, and its specific area is up to 927m
2g
-1, the macropore that is interconnected, mesoporous and micropore pore structure, and pore-size distribution is concentrated, and containing enriched in oxygen functional group, content is 12wt% ~ 17wt%.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system; Fig. 2 is the high magnification SEM photo of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system; Fig. 3 is the low range TEM photo of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system; Fig. 4 is the high magnification TEM photo of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system; Fig. 5 is the nitrogen adsorption desorption curve of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system; Fig. 6 is the wide-angle XRD spectra of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system; Fig. 7 is the total spectrogram of XPS of the standby corn scytoblastema three-dimensional multistage pore structure material with carbon element of detailed description of the invention tripartite legal system.
Detailed description of the invention
Detailed description of the invention one: in present embodiment, the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element carries out in the steps below:
Step one, maize peel is cut into fractionlet, dries under 100 DEG C of conditions after washing;
Step 2,5g is added 100mL mass concentration through the maize peel that step one processes is in the KOH solution of 5%, the 4h that then refluxes in 80 DEG C of water-baths (obtaining brown colloidal liquid), with 200 order stainless steel screen filtration after cooling, leaves solid;
Step 3, the solid that step 2 obtains is dried and is placed in quartz tube furnace under 100 DEG C of conditions, roasting 2h (gray solid) under high pure nitrogen (volume fraction is purity is 99.999%) atmosphere, temperature are 800 DEG C of conditions;
Step 4, be then hydrochloric acid solution cleaning (object be remove sylvite) of 2mol/L by concentration, centrifugal, under 120 DEG C of conditions, dry 12h after washing three times; Namely corn scytoblastema three-dimensional multistage pore structure material with carbon element is obtained.
It is 928m that present embodiment obtains corn scytoblastema three-dimensional multistage pore structure material with carbon element specific area
2g
-1, enriched in oxygen functional group content is 14.6wt%.
Detailed description of the invention two: in present embodiment, the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element carries out in the steps below:
Step one, maize peel is cut into fractionlet, dries under 100 DEG C of conditions after washing;
Step 2,5g is added 100mL mass concentration through the maize peel that step one processes is in the KOH solution of 7%, the 4h that then refluxes in 80 DEG C of water-baths (obtaining brown colloidal liquid), with 200 order stainless steel screen filtration after cooling, leaves solid;
Step 3, the solid that step 2 obtains is dried and is placed in quartz tube furnace under 100 DEG C of conditions, roasting 2h (gray solid) under high pure nitrogen (volume fraction is purity is 99.999%) atmosphere, temperature are 800 DEG C of conditions;
Step 4, be then hydrochloric acid solution cleaning (object be remove sylvite) of 2mol/L by concentration, centrifugal, under 120 DEG C of conditions, dry 12h after washing three times; Namely corn scytoblastema three-dimensional multistage pore structure material with carbon element is obtained.
It is 867m that present embodiment obtains corn scytoblastema three-dimensional multistage pore structure material with carbon element specific area
2g
-1, enriched in oxygen functional group content is 12.7wt%.
Detailed description of the invention three: in present embodiment, the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element carries out in the steps below:
Step one, maize peel is cut into fractionlet, dries under 100 DEG C of conditions after washing;
Step 2,5g is added 100mL mass concentration through the maize peel that step one processes is in the KOH solution of 9%, the 4h that then refluxes in 80 DEG C of water-baths (obtaining brown colloidal liquid), with 200 order stainless steel screen filtration after cooling, leaves solid;
Step 3, the solid that step 2 obtains is dried and is placed in quartz tube furnace under 100 DEG C of conditions, roasting 2h (gray solid) under high pure nitrogen (volume fraction is purity is 99.999%) atmosphere, temperature are 800 DEG C of conditions;
Step 4, be then hydrochloric acid solution cleaning (object be remove sylvite) of 2mol/L by concentration, centrifugal, under 120 DEG C of conditions, dry 12h after washing three times; Namely corn scytoblastema three-dimensional multistage pore structure material with carbon element is obtained.
It is 814m that present embodiment obtains corn scytoblastema three-dimensional multistage pore structure material with carbon element specific area
2g
-1, enriched in oxygen functional group content is 17.01wt%.
Test corn scytoblastema three-dimensional multistage pore structure material with carbon element prepared by present embodiment, structure as shown in figs. 1-7.
As shown in Figure 1, the porous carbon materials prepared by maize peel presents three-dimensional frame structure, has the macroporous structure be interconnected, and the thickness of hole wall is about hundreds of nanometer; From large multiplying power surface sweeping Electronic Speculum Fig. 2, hole wall surface is coarse, is to be piled up by numerous nano particle to form, and the diameter of nano particle is about 10nm.
As seen from Figure 3, the hole wall of three-dimensional multistage hole carbon has the micron flakes pattern of porous, containing a small amount of macropore, a large amount of mesoporous.Can be found out by high magnification TEM Fig. 4, large hole wall fills micropore by a large amount of cracks and turbostratic graphite carbon forms, and occurs unordered graphite lattice fringe in the edge of carbon.
As seen from Figure 5, the nitrogen adsorption desorption isotherm of this material is I/IV compound thermoisopleth, shows that this porous carbon materials contains a large amount of micropores and structure.Occurred obvious hysteresis loop at relative partial pressure more than 0.4, this hysteresis loop is H3 type lag loop, and is more than 0.95 occurred significant adsorption phenomena at relative partial pressure, illustrates that this material with carbon element contains the mesoporous and macropore of a large amount of crack shapes.
As seen from Figure 6, it is (002), (101) crystal face of two diffraction maximums corresponding graphite respectively of 20 ° and 43.8 ° at 2 θ, show to there is graphite microcrystalline structure in this material with carbon element, but (002) diffraction maximum of crystal face is relatively wide more weak with peak intensity, illustrating that the unordered degree between carbon-coating is comparatively large, is amorphous carbon.
As shown in Figure 7, main containing C, O and N tri-kinds of elements in the three-dimensional multistage pore structure material with carbon element of present embodiment.
Claims (10)
1. corn scytoblastema three-dimensional multistage pore structure material with carbon element, it is characterized in that corn scytoblastema three-dimensional multistage pore structure material with carbon element is successively through shredding, washing process post-drying by maize peel, then add in KOH solution, reflux under water bath condition again, sieve after cooling, then by solid roasting under high pure nitrogen atmosphere, then successively through hydrochloric acid solution cleaning, centrifugal, washing and drying and processing.
2. corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 1, is characterized in that by the mass ratio of maize peel and KOH solution be 1:(10 ~ 20) maize peel adds in KOH solution by proportioning.
3. corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 1 or 2, is characterized in that the concentration of KOH solution is 2% ~ 10%.
4. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element, is characterized in that the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element carries out in the steps below:
Step one, maize peel to be shredded, dry under 100 DEG C of conditions after washing;
Step 2, be that the maize peel processed through step one is added mass concentration is in the KOH solution of 2% ~ 10% to 1 ﹕ (10 ~ 20) proportioning by the mass ratio of maize peel and KOH solution, then reflux 2h ~ 6h in 60 DEG C ~ 120 DEG C water-baths, with 200 order stainless steel screen filtration after cooling, leave solid;
Step 3, solid step 2 obtained are dried and are placed in quartz tube furnace, roasting 1 ~ 2h under high pure nitrogen atmosphere, temperature are 600 ~ 1000 DEG C of conditions;
Step 4 is then with hydrochloric acid solution cleaning, centrifugal, washed several times with water post-drying; Namely corn scytoblastema three-dimensional multistage pore structure material with carbon element is obtained.
5. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 4, is characterized in that KOH solution mass concentration described in step 2 is 5% ~ 9%.
6. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 4, is characterized in that KOH solution mass concentration described in step 2 is 7%.
7. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 4, is characterized in that bake out temperature described in step 3 is 100 DEG C.
8. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 4, it is characterized in that the sintering temperature described in step 3 is 800 DEG C, roasting time is 2 hours.
9. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 4, is characterized in that the concentration of hydrochloric acid solution described in step 4 is 2mol/L.
10. the preparation method of corn scytoblastema three-dimensional multistage pore structure material with carbon element according to claim 4, it is characterized in that bake out temperature described in step 4 is 120 DEG C, drying time is 12h.
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Cited By (4)
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| CN106311224A (en) * | 2016-09-10 | 2017-01-11 | 上海大学 | Preparation method of charcoal-based oxygen reduction catalyst |
| CN112403435A (en) * | 2019-08-21 | 2021-02-26 | 天津科技大学 | Preparation method of KOH-microwave activated corncob activated carbon for treating cationic dye-containing wastewater |
| WO2022052539A1 (en) * | 2020-09-10 | 2022-03-17 | 中国矿业大学 | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
| CN116440868A (en) * | 2023-04-18 | 2023-07-18 | 内蒙古大学 | Preparation method of in-situ nitrogen-doped caragana microphylla porous biochar material |
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| CN104445193A (en) * | 2014-12-03 | 2015-03-25 | 盐城工学院 | Branch and leaf porous carbon with function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as preparation method and application thereof |
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| CN1446748A (en) * | 2003-03-07 | 2003-10-08 | 太原理工大学 | Method for preparing active carbon with height ratio surface area |
| CN104709906A (en) * | 2013-12-17 | 2015-06-17 | 中国科学院过程工程研究所 | Preparation method of three dimensional graded porous activated carbon material |
| CN104445193A (en) * | 2014-12-03 | 2015-03-25 | 盐城工学院 | Branch and leaf porous carbon with function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311224A (en) * | 2016-09-10 | 2017-01-11 | 上海大学 | Preparation method of charcoal-based oxygen reduction catalyst |
| CN112403435A (en) * | 2019-08-21 | 2021-02-26 | 天津科技大学 | Preparation method of KOH-microwave activated corncob activated carbon for treating cationic dye-containing wastewater |
| WO2022052539A1 (en) * | 2020-09-10 | 2022-03-17 | 中国矿业大学 | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
| GB2603717A (en) * | 2020-09-10 | 2022-08-10 | Univ China Mining | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
| GB2603717B (en) * | 2020-09-10 | 2023-03-22 | Univ China Mining | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
| CN116440868A (en) * | 2023-04-18 | 2023-07-18 | 内蒙古大学 | Preparation method of in-situ nitrogen-doped caragana microphylla porous biochar material |
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