CN115477298B - Hollow spherical super-structure carbon material and preparation method and application thereof - Google Patents
Hollow spherical super-structure carbon material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 13
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 23
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 8
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 6
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 6
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 229920000867 polyelectrolyte Polymers 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000012065 filter cake Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 238000005406 washing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910052844 willemite Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical compound OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 2
- 229960003052 roxarsone Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LVKZSFMYNWRPJX-UHFFFAOYSA-N benzenearsonic acid Natural products O[As](O)(=O)C1=CC=CC=C1 LVKZSFMYNWRPJX-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a hollow spherical superstructure carbon material and a preparation method thereof, belonging to the technical field of adsorption material preparation, wherein the method comprises the following steps: (1) The biomass sugar, the structure directing agent and the dispersing agent are dispersed and mixed and then subjected to hydrothermal reaction to prepare hydrothermal carbon; wherein the structure directing agent is fatty acid methyl ester ethoxylate, and the mass ratio of the sugar to the structure directing agent and the dispersing agent is (3-9): (0.02-0.05): (0.05-0.1); (2) And mixing the hydrothermal carbon with sodium oxalate, and calcining at high temperature under a protective atmosphere to obtain the hollow spherical super-structure carbon material. The invention takes biomass sugar as a raw material, and prepares the hollow super-structure carbon material by adding high cloud point fatty acid methyl ester polyoxyethylene ether and polyelectrolyte to assist in hydrothermal reaction, and the prepared super-structure carbon material has a hollow structure and better dispersibility.
Description
Technical Field
The invention relates to the technical field of preparation of adsorption materials, in particular to a hollow spherical super-structure carbon material, and a preparation method and application thereof.
Background
The carbon material has the characteristics of adjustable structure, excellent thermodynamic stability and the like, and is widely used as a catalyst carrier, an electrochemical material, an energy storage and adsorption material and the like. The micro/nano-scale spherical super-structure carbon material assembled by the nano elements not only inherits the performance of the nano elements, but also obtains certain unconventional characteristics. For example, spherical MOF nanorods are used as self-templates, and super-structure spherical carbon materials assembled by the nanorods are prepared by pyrolysis, the super-structure spherical carbon materials have large specific surface area (2350 m < 2 >/g) and pore volume (2.0 cm < 3 >/g), and the super-structure spherical carbon materials loaded with ultrafine Pd particles have excellent catalytic activity on formic acid dehydrogenation (Advanced Materials,2019,31,1900440).
Biomass-derived carbohydrates are common raw materials for the preparation of carbon materials. At present, common methods for preparing carbon materials by taking biomass sugar as a raw material include a pyrolysis method, a hard template method, a soft template method, a hydrothermal method and the like. The hydrothermal method has the advantages of low energy consumption, simplicity and convenience in operation, and the prepared carbon material surface is rich in oxygen-containing functional groups. And proper additives are introduced in the hydrothermal process, so that the morphology regulation and control of the carbon material can be realized. For example, nickel acetate has multiple functions such as structure guiding, catalytic graphitization, pore-forming and the like, and spherical super-structure mesoporous carbon materials (Journal of Materials Chemistry A,2014,2,16884-16891) assembled by petal pieces with the thickness of 20nm can be prepared by adding nickel acetate into a glucose solution and performing steps such as hydrothermal carbonization, pyrolysis, etching and the like. Li et al (Carbon, 2021,176,1-10) propose the idea of using an interlayer growth strategy to prepare Carbon superstructure materials. The zinc gluconate is used as a carbon source, silicon dioxide is added in the hydrothermal process, the formation of a C/Zn2SiO4 sheet composite is facilitated, the C/Zn2SiO4 sheet continuously captures spherical silicon dioxide, and finally the C/Zn2SiO4 super-structure composite material with an alternating structure is formed. Carbonizing and HF washing the C/Zn2SiO4 composite material to obtain the spherical super-structure carbon material composed of nano sheets with the thickness less than 1 nm. The addition of acrylic acid to glucose solution can give spherical carbon superstructures (Chemistry of Materials,2009,21,484-490;Angewandte Chemie International Edition,2017,56,600-604;Materials Letters,2017,193,172-175;Chemical Engineering Journal,2018,338,734-744), however, the superstructural carbon spheres prepared by this method have poor dispersibility. At present, spherical carbon superstructures prepared from biomass are mainly solid, and hollow spherical carbon superstructures are still rarely reported.
Disclosure of Invention
The invention aims at solving the problems by providing a hollow spherical super-structure carbon material and a preparation method and application thereof.
The aim of the invention is realized by adopting the following technical scheme:
the preparation method of the hollow spherical super-structure carbon material comprises the following steps:
(1) The biomass sugar, the structure directing agent and the dispersing agent are dispersed and mixed and then subjected to hydrothermal reaction to prepare hydrothermal carbon; wherein the structure directing agent is fatty acid methyl ester ethoxylate, and the mass ratio of the sugar to the structure directing agent and the dispersing agent is (3-9): (0.02-0.05): (0.05-0.1);
(2) Mixing the hydrothermal carbon with an activating agent sodium oxalate, and calcining at a high temperature in a protective atmosphere to obtain the hollow spherical super-structure carbon material; wherein the mass ratio of the hydrothermal carbon to the sodium oxalate is 1: (1-5).
As a further preferred embodiment of the present invention, the sugar is one or more of xylose, ribose and arabinose.
As a further preferred embodiment of the present invention, the dispersant is sodium polyacrylate and/or sodium poly (4-styrenesulfonic acid-co-maleic acid) salt.
As a further preferred embodiment of the invention, the sugar is present in the water in a mass concentration of 5-15wt%, more preferably 5wt%.
As a further preferred embodiment of the present invention, the reaction temperature of the hydrothermal reaction is 140-180 ℃ and the reaction time is 9-18h.
As a further preferable embodiment of the invention, the temperature rising rate of the high-temperature calcination is 1-5 ℃/min, the calcination temperature is 500-900 ℃ and the calcination time is 1-5h.
Another object of the present invention is to provide a hollow sphere-shaped super-structure carbon material, which is prepared by the aforementioned preparation method.
Still another object of the present invention is to provide a method for applying the hollow spherical super-structure carbon material, specifically for adsorbing organic arsenic in a water body, and more preferably for adsorbing para-amino phenylarsonic acid and/or roxarsone in a water body.
The beneficial effects of the invention are as follows:
(1) The invention takes biomass sugar as a raw material, and prepares the hollow super-structure carbon material by adding high cloud point fatty acid methyl ester polyoxyethylene ether and polyelectrolyte to assist hydrothermal reaction, the prepared super-structure carbon material is of a hollow structure and has good dispersibility, the particle diameter is 1-6 mu m, the cavity diameter is 100-1200 nm, the wall thickness is 100-900 nm, and the hollow spherical super-structure carbon material (SAC) obtained after activation treatment maintains the original shape and cavity structure, the particle diameter is 1-2.5 mu m, the cavity diameter is 600-1200 nm, and the wall thickness is 200-400 nm. Specifically, fatty acid methyl ester polyoxyethylene ether and biomass sugar firstly form spherical micelle in a solution, sugar molecules form a carbon core intermediate through the steps of dehydration, condensation, polymerization and the like in the hydrothermal process, and polyelectrolyte is adsorbed on the surface of the carbon core intermediate to strengthen the steric hindrance and electrostatic repulsion and inhibit the growth of the polyelectrolyte due to high surface energy of the carbon core intermediate, so that the assembly on the surface of the micelle is promoted; along with the prolongation of the hydrothermal carbonization time, the quantity of the carbon core intermediates is increased, the high surface energy promotes the intermolecular dehydration, aldol condensation and other reactions of the newly generated carbon cores and the carbon cores, and finally, the spherical super-structure hollow carbon material with good dispersibility is formed; compared with other polyether surfactants, the fatty acid methyl ester polyoxyethylene ether has higher cloud point, still keeps a spherical micelle structure in a hydrothermal environment, and is beneficial to the assembly of nano carbon core particles on the surface and the formation of hollow super-structure carbon materials.
(2) The preparation method of the spherical super-structure carbon material provided by the invention has the advantages of simple process, environment friendliness and taking the renewable biomass derivative as a raw material.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is an SEM image of (a) a hollow-superstructure hydrothermal carbon material, (b) SAC-1, prepared in example 1 of the present invention;
FIG. 2 is a TEM image of (a) a hollow-superstructure hydrothermal carbon material, (b) SAC-1 prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a hollow-core superstructural hydrothermal carbon material prepared in example 2 of the present invention;
FIG. 4 is a TEM image of the hollow superstructure hydrothermal carbon material prepared in example 2 of the present invention;
FIG. 5 is an SEM image of a hollow-core superstructural hydrothermal carbon material prepared in example 3 of the present invention;
FIG. 6 is a TEM image of the hollow superstructure hydrothermal carbon material prepared in example 3 of the present invention;
FIG. 7 is an SEM image of a hollow-core superstructural hydrothermal carbon material prepared in example 4 of the present invention;
FIG. 8 is a TEM image of the hollow superstructure hydrothermal carbon material prepared in example 4 of the present invention;
FIG. 9 is an SEM image of the hydrothermal carbon material prepared in comparative example 1 of the present invention;
FIG. 10 is a TEM image of the hydrothermal carbon material prepared in comparative example 1 of the present invention;
FIG. 11 is an SEM image of the hydrothermal carbon material prepared in comparative example 2 of the present invention;
FIG. 12 is a TEM image of the hydrothermal carbon material prepared in comparative example 2 of the present invention;
FIG. 13 is an SEM image of the hydrothermal carbon material prepared in comparative example 3 of the present invention;
fig. 14 is a TEM image of the hydrothermal carbon material prepared in comparative example 3 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Materials involved in embodiments of the present invention are available from commercial sources. The amount of each component is expressed in parts by mass and volume, g/mL.
Example 1
Referring to fig. 1-2, the preparation method of the hollow spherical super-structure carbon material provided by the embodiment comprises the following steps:
(1) 3 parts by mass of ribose, 0.02 part by mass of fatty acid methyl ester polyoxyethylene ether and 0.05 part by mass of poly (4-styrenesulfonic acid-copolymerization-maleic acid) sodium salt are dissolved in 60 parts by volume of water, and after being stirred uniformly, the mixture is transferred into a 100 parts by volume of stainless steel water heating kettle with polytetrafluoroethylene lining, and the mixture is placed in an air drying oven to be subjected to hydrothermal reaction for 12 hours at 160 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed three times by water and ethanol, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain black powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared by the embodiment is shown in the attached figures 1-2; as can be seen from the figure 1 (a), the prepared hydrothermal carbon has a spherical structure, has rough surface and wrinkles, and has a particle size distribution range of 0.7-2.8 mu m; as can be seen from FIG. 2 (a), the prepared hydrothermal carbon has a hollow structure, the diameter of the hollow cavity is about 200-1000 nm, and the wall thickness is about 100-500 nm;
(2) Taking 1 part by mass of the hydrothermal carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, regulating the flow of the nitrogen to be 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, washing a filter cake with water to be neutral, and drying the filter cake in a hot air oven at 60 ℃ for 12 hours to obtain the hollow spherical super-structure carbon material named SAC-1. As can be seen from FIG. 1 (b) and FIG. 2 (b), SAC-1 maintains the original morphology and cavity structure, the particle size ranges from 1 to 2.5 μm, the cavity diameter ranges from 600 to 1200nm, and the wall thickness ranges from 200 to 400nm.
Example 2
The embodiment of the invention provides a hollow spherical super-structure carbon material based on the embodiment 1, and the preparation method comprises the following steps:
(1) 3 parts by mass of arabinose, 0.05 part by mass of fatty acid methyl ester polyoxyethylene ether and 0.05 part by mass of sodium polyacrylate are dissolved in 60 parts by volume of water, and after being stirred uniformly, the mixture is transferred into a 100 parts by volume of stainless steel water heating kettle lined with polytetrafluoroethylene, and the mixture is placed in a blast drying box for hydrothermal reaction for 12 hours at 160 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed three times by water and ethanol, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain black powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared by the method is shown in figures 3-4; as can be seen from FIG. 3, the prepared hydrothermal carbon has a spherical structure, and the particle size distribution range is 0.8-3.0 μm; as can be seen from FIG. 4, the prepared hydrothermal carbon has both a solid structure and a hollow structure, wherein the hollow structure has a cavity diameter of about 2.0-3.0 μm and a wall thickness of about 500-800 nm;
(2) Taking 1 part by mass of the hydrothermal carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, regulating the flow of the nitrogen to be 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, washing the filter cake with water to be neutral, and drying the filter cake in a hot air oven at 60 ℃ for 12 hours to obtain the hollow spherical super-structure carbon material, wherein the hollow spherical super-structure carbon material is named SAC-2.
Example 3
The embodiment of the invention provides a hollow spherical super-structure carbon material based on the embodiment 1-2, and the preparation method comprises the following steps:
(1) 6 parts by mass of xylose, 0.02 part by mass of fatty acid methyl ester polyoxyethylene ether and 0.07 part by mass of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt are dissolved in 60 parts by volume of water, and after being uniformly stirred, the mixture is transferred into a 100 parts by volume of stainless steel water heating kettle with polytetrafluoroethylene lining, and the mixture is placed in a blast drying box for hydrothermal reaction for 18 hours at 140 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed three times by water and ethanol, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain black powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared by the method is shown in figures 5-6; as can be seen from FIG. 5, the prepared hydrothermal carbon has a spherical structure, and the particle size distribution range is 1.0-3.0 μm; as can be seen from FIG. 6, the prepared hydrothermal carbon has a hollow structure, the diameter of the cavity is about 1.0-1.2 μm, and the wall thickness is about 200-500 nm;
(2) Taking 1 part by mass of the hydrothermal carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, regulating the flow of the nitrogen to be 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, washing the filter cake with water to be neutral, and drying the filter cake in a hot air oven at 60 ℃ for 12 hours to obtain the hollow spherical super-structure carbon material, wherein the hollow spherical super-structure carbon material is named SAC-3.
Example 4
The embodiment of the invention provides a hollow spherical super-structure carbon material based on the embodiment 1-3, and the preparation method comprises the following steps:
(1) 9 parts by mass of xylose, 0.02 part by mass of fatty acid methyl ester polyoxyethylene ether and 0.10 part by mass of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt are dissolved in 60 parts by volume of water, and after being uniformly stirred, the mixture is transferred into a 100 parts by volume of stainless steel water heating kettle with polytetrafluoroethylene lining, and the mixture is placed in a blast drying box for hydrothermal reaction for 9 hours at 180 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed three times by water and ethanol, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain black powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared by the method is shown in figures 7-8; as can be seen from FIG. 7, the prepared hydrothermal carbon has a spherical structure, and the particle size distribution range is 0.5-3.4 μm; as can be seen from FIG. 8, the prepared hydrothermal carbon has both a solid structure and a hollow structure, the diameter of the hollow cavity is about 200-500 nm, and the wall thickness is about 0.9-1.5 μm;
(2) Taking 1 part by mass of the hydrothermal carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, regulating the flow of the nitrogen to be 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, washing the filter cake with water to be neutral, and drying the filter cake in a hot air oven at 60 ℃ for 12 hours to obtain the hollow spherical super-structure carbon material named SAC-4.
Comparative example 1
A carbon material, the method of making comprising the steps of:
(1) 3 parts by mass of ribose and 0.05 part by mass of fatty acid methyl ester polyoxyethylene ether are dissolved in 60 parts by volume of water, and after being stirred uniformly, the mixture is transferred into a stainless steel water heating kettle with 100 parts by volume of polytetrafluoroethylene lining, and the stainless steel water heating kettle is placed in an air blast drying box and subjected to hydrothermal reaction for 12 hours at 160 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed three times by water and ethanol, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain black powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared in the comparative example is shown in figures 9-10; as can be seen from FIG. 9, the hydrothermal carbon has a spherical structure with a particle size of 0.3-1.7 μm; as can be seen from FIG. 10, the prepared hydrothermal carbon has a hollow structure, the diameter of the cavity is about 100-400 nm, and the wall thickness is about 150-350 nm;
(2) Taking 1 part by mass of a hot carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, adjusting the flow rate of the nitrogen to 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, and washing a filter cake with water to neutrality. The cake was dried in a hot air oven at 60℃for 12h to give the final product, designated AC-1.
Comparative example 2
A carbon material, the method of making comprising the steps of:
(1) 3 parts by mass of ribose and 0.05 part by mass of poly (4-styrenesulfonic acid-copolymerization-maleic acid) sodium salt are dissolved in 60 parts by volume of water, and after being stirred uniformly, the solution is transferred into a stainless steel water heating kettle with 100 parts by volume of polytetrafluoroethylene lining, and the solution is placed in a blast drying box for hydrothermal reaction for 12 hours at 160 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed three times by water and ethanol, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain black powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared in the comparative example is shown in figures 11-12; as can be seen from FIG. 11, the hydrothermal carbon has a spherical structure with a particle size ranging from 0.3 to 0.9 μm; as can be seen from fig. 12, the prepared hydrothermal carbon has a solid structure;
(2) Taking 1 part by mass of a hot carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, adjusting the flow rate of the nitrogen to 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, and washing a filter cake with water to neutrality. The cake was dried in a hot air oven at 60℃for 12h to give the final product, designated AC-2.
Comparative example 3
A carbon material, the method of making comprising the steps of:
(1) 3 parts by mass of ribose are dissolved in 60 parts by volume of water, stirred uniformly and then transferred into 100 parts by volume of stainless steel water heating kettle lined with polytetrafluoroethylene, placed in a blast drying box and subjected to hydrothermal reaction for 12 hours at 160 ℃; after the product is cooled to room temperature, the obtained suspension is filtered, the filter cake is respectively washed with water and ethanol for three times, and the filter cake is dried for 24 hours at 60 ℃ in an oven to obtain brown powdery hydrothermal carbon;
the apparent morphology of the hydrothermal carbon prepared in the comparative example is shown in figures 13-14; as can be seen from FIG. 13, the hydrothermal carbon has a spherical structure with a particle size ranging from 0.15 to 0.60 μm; as can be seen from fig. 14, the prepared hydrothermal carbon has a solid structure;
(2) Taking 1 part by mass of a hot carbon sample, uniformly mixing with 3 parts by mass of sodium oxalate, transferring into a ceramic boat, placing into a tube furnace, introducing nitrogen to replace air in the furnace, adjusting the flow rate of the nitrogen to 50mL/min, heating to 700 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours, naturally cooling to room temperature, washing the roasted black powder with 60 parts by volume of 1.0mol/L HCl solution, filtering, and washing a filter cake with water to neutrality. The cake was dried in a hot air oven at 60℃for 12h to give the final product, designated AC-3.
Specific surface areas, pore structures, and organic arsenic adsorption amounts data of the carbon materials prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in table 1:
table 1 pore structures and organic arsenic adsorption amounts of the carbon materials described in examples and comparative examples
As can be seen from Table 1, the SAC-series carbon materials prepared according to examples 1 to 4 of the present invention have a relatively high total specific surface area and micropore volume, up to 847.02m2/g and 0.33cm3/g, respectively, and adsorption capacities of p-aminophenylarsonic acid and roxarsone are up to 268.18mg/g and 413.38mg/g, respectively. Thus, the SAC prepared by the invention is a very promising organic arsenic adsorbing material.
According to the embodiment of the invention, biomass sugar is used as a raw material, and the hollow super-structure carbon material is prepared by adding high-cloud-point fatty acid methyl ester polyoxyethylene ether and polyelectrolyte to assist in hydrothermal reaction, so that the prepared super-structure carbon material has a hollow structure and good dispersibility.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (3)
1. The preparation method of the hollow spherical super-structure carbon material is characterized by comprising the following steps of:
(1) The biomass sugar, the structure directing agent and the dispersing agent are dispersed and mixed and then subjected to hydrothermal reaction to prepare hydrothermal carbon; wherein the structure directing agent is fatty acid methyl ester ethoxylate, and the mass ratio of the sugar to the structure directing agent and the dispersing agent is (3-9): (0.02-0.05): (0.05-0.1);
(2) Mixing the hydrothermal carbon with an activating agent sodium oxalate, and calcining at a high temperature in a protective atmosphere to obtain the hollow spherical super-structure carbon material; wherein the mass ratio of the hydrothermal carbon to the sodium oxalate is 1: (1-5);
the dispersing agent is sodium polyacrylate and/or poly (4-styrenesulfonic acid-co-maleic acid) sodium salt;
the reaction temperature of the hydrothermal reaction is 140-180 ℃ and the reaction time is 9-18h;
the high-temperature calcination has a heating rate of 1-5 ℃/min, a calcination temperature of 500-900 ℃ and a calcination time of 1-5h.
2. The method for producing a hollow spherical superstructure carbon material according to claim 1, wherein the sugar is one or more of xylose, ribose, and arabinose.
3. The method for producing a hollow sphere-shaped super structure carbon material according to claim 1, wherein the mass concentration of the sugar in water is 5 to 15wt%.
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