Additive-assisted hydrothermal route to synthesize nanoporous carbon microspheres with controlled particle size
Shun-jian XU1,2,*()
1 School of Mechanical and Electrical Engineering, Xinyu University, Xinyu 338004, Jiangxi, China 2 Xinyu Institute of New Energy, Xinyu University, Xinyu 338004, Jiangxi, China
Carbon microspheres were synthesized by the hydrothermal treatment of saccharides (fructose and starch) in the presence of additives (HCl and KCl) and the subsequent pyrolysis, and the role of the additives in the hydrothermal reaction was also investigated. The results show that carbon microspheres with well-developed nanoporous structures and surface oxygen functional groups are obtained. Both of the additives in the saccharide solutions induce the enlargement of the size of the microspheres. The mean diameter of the microspheres can be tailored in a range from 0.53μm to 6.67μm. The morphology of the microspheres depends on the reaction kinetics during hydrothermal treatment. During pyrolysis, the microstructure of the microspheres is transformed from polymer to glassy carbon, which is accompanied by a mass loss of about 50% and a contraction of over 20% in scale. Both of the additives display distinct effects on the stages of the hydrothermal reaction of the saccharide solutions. The HCl mainly accelerates the hydrolysis kinetic of polysaccharide and the dehydration and fragmentation of monosaccharide, while the KCl chiefly enhances the growth kinetic of the microspheres. The growth of the microspheres is performed through two main ways:the reactive oxygen functionalities present in both the surfaces of the microspheres and the building units and the merged fine microspheres.
SUN H C , CHEN T Q , LIU Y , et al. Carbon microspheres via microwave-assisted synthesis as counter electrodes of dye-sensi-tized solar cells[J]. Journal of Colloid and Interface Science, 2015, 445, 326- 329.
doi: 10.1016/j.jcis.2015.01.016
2
SUN Y , YANG G , WEN C , et al. Preparation of carbon sphere from lactose by hydrothermal reaction and its performance in gas separation[J]. Environmental Progress & Sustainable Energy, 2014, 33 (2): 581- 587.
NIU M , YANG Y R , WANG X , et al. Preparation and charac-terization of flame retardant PET fiber with microencapsulated CMSs/PET[J]. Journal of Materials Engineering, 2016, 44 (6): 63- 69.
CHENG Y L , LI T H , LI F J , et al. Preparation of mesocarbon microbeads with silicone oil/pitch emulsion[J]. Journal of Mate-rials Engineering, 2010, (3): 56- 59.
5
BERL E , SCHMIDT A , KOCH H . The origin of coal[J]. Angewandte Chemie, 1932, 45 (32): 517- 519.
doi: 10.1002/(ISSN)1521-3757
6
WANG Q , LI H , CHEN L Q , et al. Monodispersed hard carbon spherules with uniform nanopores[J]. Carbon, 2001, 39 (14): 2211- 2214.
doi: 10.1016/S0008-6223(01)00040-9
7
SEVILLA M , FUERTES A B . Chemical and structural proper-ties of carbonaceous products obtained by hydrothermal carboni-zation of saccharides[J]. European Journal of Chemistry, 2009, 15 (16): 4195- 4203.
doi: 10.1002/chem.v15:16
8
YAO C , SHIN Y , WANG L , et al. Hydrothermal dehydration of aqueous fructose solutions in a closed system[J]. The Journal of Physical Chemistry C, 2007, 111 (42): 15141- 15145.
doi: 10.1021/jp074188l
9
SUN X M , LI Y D . Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles[J]. Angewandte Che-mie International Edition, 2004, 43 (5): 597- 601.
doi: 10.1002/(ISSN)1521-3773
10
QI Y , ZHANG M , QI L , et al. Mechanism for the formation and growth of carbonaceous spheres from sucrose by hydrothermal carbonization[J]. RSC Advances, 2016, 6 (26): 20814- 20823.
11
SHIN Y S , WANG L Q , BAE I T , et al. Hydrothermal synth-eses of colloidal carbon spheres from cyclodextrins[J]. The Journal of Physical Chemistry C, 2008, 112 (37): 14236- 14240.
doi: 10.1021/jp801343y
12
OKANO T , SUZUKI Y . Hydrothermal synthesis of carbonace-ous spheres starting from different starches[J]. Journal of the Ceramic Society of Japan, 2016, 124 (1): 79- 81.
doi: 10.2109/jcersj2.15111
13
ZHENG M T , LIU Y L , JIANG K M , et al. Alcohol-assisted hydrothermal carbonization to fabricate spheroidal carbons with a tunable shape and aspect ratio[J]. Carbon, 2010, 48 (4): 1224- 1233.
doi: 10.1016/j.carbon.2009.11.045
14
RYU J , SUH Y W , SUH D J , et al. Hydrothermal preparation of carbon microspheres from mono-saccharides and phenolic com-pounds[J]. Carbon, 2010, 48 (7): 1990- 1998.
doi: 10.1016/j.carbon.2010.02.006
15
DEMIR-CAKAN R , BACCILE N , ANTONIETTI M . Carboxy-late-rich carbonaceous materials via one-step hydrothermal carb-onization of glucose in the presence of acrylic acid[J]. Chemis-try of Materials, 2009, 21 (3): 484- 490.
doi: 10.1021/cm802141h
16
MOON G H , SHIN Y S , AREV B W , et al. Carbon dioxide-assisted fabrication of highly uniform submicron-sized colloidal carbon spheres via hydrothermal carbonization using soft drink[J]. Colloid and Polymer Science, 2012, 290 (15): 1567- 1573.
doi: 10.1007/s00396-012-2729-4
17
CUI X J , ANTONIETTI M , YU S H . Structural effects of iron oxide nanoparticles and iron ions on the hydrothermal carboniza-tion of starch and rice carbohydrates[J]. Small, 2006, 2 (6): 756- 759.
doi: 10.1002/(ISSN)1613-6829
18
CAI H M , LIN X Y , TIAN L Y , et al. One-step hydrothermal synthesis of carbonaceous spheres from glucose with an alum-inum chloride catalyst and its adsorption characteristic for Uranium(Ⅵ)[J]. Industrial & Engineering Chemistry Resear-ch, 2016, 55 (36): 9648- 9656.
19
TANABE Y , YAMANAKA J , HOSHI K , et al. Surface grap-hitization of furan-resin-derived carbon[J]. Carbon, 2001, 39 (15): 2347- 2353.
doi: 10.1016/S0008-6223(01)00069-0
20
BRAUN A , BARTSCH M , SCHNYDER B , et al. X-ray scat-tering and adsorption studies of thermally oxidized glassy carbon[J]. Journal of Non-Crystalline Solids, 1999, 260 (1/2): 1- 14.
21
LI M , LI W , LIU S X . Control of the morphology and chemical properties of carbon spheres prepared from glucose by a hydr-othermal method[J]. Journal of Materials Research, 2012, 27 (8): 1117- 1123.
doi: 10.1557/jmr.2011.447
22
SING K S W . Reporting physisorption data for gas/solid syst-ems with special reference to the determination of surface-area and porosity[J]. Pure and Applied Chemistry, 1985, 57 (4): 603- 619.
doi: 10.1351/pac198557040603
23
YAO W T , YU L , YAO P F , et al. Bulk production of nonpre-cious metal catalysts from cheap starch as precursor and their excellent electrochemical activity[J]. ACS Sustainable Chem-istry & Engineering, 2016, 4 (6): 3235- 3244.
24
LI M , LI W , LIU S . Hydrothermal synthesis, characterization, and KOH activation of carbon spheres from glucose[J]. Carb-ohydrate Research, 2011, 346 (8): 999- 1004.
doi: 10.1016/j.carres.2011.03.020
25
GARROTE G , DOMINGUEZ H , PARAJO J C . Hydrothermal processing of lignocellulosic materials[J]. Holz als Roh-und Werkstoff, 1999, 57 (3): 191- 202.
doi: 10.1007/s001070050039
26
NAGAMORI M , FUNAZUKURI T . Glucose production by hydrolysis of starch under hydrothermal conditions[J]. Journal of Chemical Technology & Biotechnology, 2004, 79 (3): 229- 233.
27
SAKAKI T , SHIBATA M , MILI T , et al. Reaction model of cellulose decomposition in near-critical water and fermentation of products[J]. Bioresource Technology, 1996, 58 (2): 197- 202.
doi: 10.1016/S0960-8524(96)00099-5
28
TANGER Ⅳ C , PITZER K S . Calculation of the ionization con-stant of H2O to 2, 273K and 500MPa[J]. AIChE Journal, 1989, 35 (10): 1631- 1638.
doi: 10.1002/(ISSN)1547-5905
2019, Vol. 47 
)
