Please wait a minute...

Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2020, Vol. 14 Issue (6) : 1072-1086
Facile preparation of polybenzoxazine-based carbon microspheres with nitrogen functionalities: effects of mixed solvents on pore structure and supercapacitive performance
Uthen Thubsuang1(), Suphawadee Chotirut1, Apisit Thongnok1, Archw Promraksa1, Mudtorlep Nisoa2, Nicharat Manmuanpom3,4, Sujitra Wongkasemjit3,4, Thanyalak Chaisuwan3,4
1. School of Engineering and Technology, Walailak University, Nakhon Si Thammarat 80160, Thailand
2. School of Science, Walailak University, Nakhon Si Thammarat 80160, Thailand
3. The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand
4. Center of Excellence on Petrochemical and Materials Technology, Bangkok 10330, Thailand
Download: PDF(4379 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

In this study, polybenzoxazine (PBZ)-based carbon microspheres were prepared via a facile method using a mixture of formaldehyde (F) and dimethylformamide (DMF) as the solvent. The PBZ microspheres were successfully obtained at the F/DMF weight ratios of 0.4 and 0.6. These microspheres exhibited high nitrogen contents after carbonization. The microstructures of all the samples showed an amorphous phase and a partial graphitic phase. The porous carbon with the F/DMF ratio of 0.4 showed significantly higher specific capacitance (275.1 Fg‒1) than the reference carbon (198.9 Fg‒1) at 0.05 Ag‒1. This can be attributed to the synergistic electrical double-layer capacitor and pseudo-capacitor behaviors of the porous carbon with the F/DMF ratio of 0.4. The presence of nitrogen/oxygen functionalities induced pseudo-capacitance in the microspheres, and hence increased their total specific capacitance. After activation with CO2, the specific surface area of the carbon microspheres with the F/DMF ratio of 0.4 increased from 349 to 859 m2g‒1 and the specific capacitance increased to 424.7 Fg‒1. This value is approximately two times higher than that of the reference carbon. The results indicated that the F/DMF ratio of 0.4 was suitable for preparing carbon microspheres with good supercapacitive performance. The nitrogen/oxygen functionalities and high specific surface area of the microspheres were responsible for their high capacitance.

Keywords PBZ      carbon      porous materials      microsphere      supercapacitor     
Corresponding Author(s): Uthen Thubsuang   
Just Accepted Date: 30 December 2019   Online First Date: 24 February 2020    Issue Date: 11 September 2020
 Cite this article:   
Uthen Thubsuang,Suphawadee Chotirut,Apisit Thongnok, et al. Facile preparation of polybenzoxazine-based carbon microspheres with nitrogen functionalities: effects of mixed solvents on pore structure and supercapacitive performance[J]. Front. Chem. Sci. Eng., 2020, 14(6): 1072-1086.
E-mail this article
E-mail Alert
Articles by authors
Uthen Thubsuang
Suphawadee Chotirut
Apisit Thongnok
Archw Promraksa
Mudtorlep Nisoa
Nicharat Manmuanpom
Sujitra Wongkasemjit
Thanyalak Chaisuwan
Fig.1  Scheme 1 Synthesis of carbon microspheres.
Fig.2  (a) FTIR spectra, (b) feasible structures, (c) DSC thermograms, and (d) TGA thermograms of MCBP and PBZ.
Fig.3  (a–e) FE-SEM images of the samples (inset: graphical model for the observed particles); (f) TEM image of AC-0.4.
Fig.4  Particle size distributions of (a) C-0.2, (b) C-0.4, (c) C-0.6, and (d) AC-0.4.
Fig.5  (a) XRD patterns and (b) Raman spectra of the as-prepared porous carbons.
Fig.6  Nitrogen adsorption-desorption isotherms for (a) C-Ref, (b) C-0.2, (c) C-0.4, (d) C-0.6, and (e) AC-0.4 and the (f) pore size distributions of all the samples.
Sample SBETa) /(m2?g-1) Vmicrob) /(cm3?g-1) Vmesoc) /(cm3?g-1) VTd) /(cm3?g-1) APSe) /nm
C-Ref 336 0.17 0.02 0.19 1.0
C-0.2 331 0.13 0.07 0.20 1.2
C-0.4 349 0.14 0.06 0.20 1.2
C-0.6 310 0.11 0.07 0.18 1.2
AC-0.4 859 0.43 0.02 0.45 1.0
Tab.1  Pore structure of the samples
Fig.7  Pore size distributions of C-Ref, C-0.2, C-0.4, and C-0.6.
Fig.8  (a) XPS N1s spectra of all the samples, (b) pseudo-Faradaic reaction of N-5 and N-6 [7,12], (c) XPS O1s spectra of all the samples, and (d) pseudo-Faradaic reaction of O-1 [12].
Sample XPS/wt-% Elemental analyzer/%
C N O C H N Other elements
C-Ref 84.8 3.4 11.8 78.6 1.8 4.2 15.4
C-0.2 88.3 4.7 7.0 77.2 1.7 5.0 16.1
C-0.4 85.3 5.0 9.7 79.5 1.7 5.4 13.4
C-0.6 79.9 5.7 14.4 79.2 1.7 5.3 13.8
AC-0.4 89.3 4.2 6.5 75.4 2.0 4.3 18.3
Tab.2  Elemental compositions of all the samples
Fig.9  (a) CV profiles of all the samples at 1 mV?s?1, (b) CV profile of C-0.4 at various scan rates, (c) GCD curves of all the samples at 0.1 A?g?1, (d) GCD curves of AC-0.4 at various current densities, (e) specific capacitance of all the samples as a function of the current density, and (f) Ragone plots for all the samples.
Fig.10  Laboratory-scale supercapacitor illuminating a red LED.
Fig.11  Nyquist plots for all the samples (a) large scale and (b) enlarged scale in the high-frequency region.
1 L L Zhang, X S Zhao. Carbon-based materials as supercapacitor electrodes. Chemical Society Reviews, 2009, 38(9): 2520–2531
2 U Thubsuang, S Laebang, N Manmuanpom, S Wongkasemjit, T Chaisuwan. Tuning pore characteristics of porous carbon monoliths prepared from rubber wood waste treated with H3PO4 or NaOH and their potential as supercapacitor electrode materials. Journal of Materials Science, 2017, 52(11): 6837–6855
3 W Lei, J Guo, Z Wu, C Xuan, W Xiao, D Wang. Highly nitrogen and sulfur dual-doped carbon microspheres for supercapacitors. Science Bulletin, 2017, 62(14): 1011–1017
4 D Zhu, Y Wang, L Gan, M Liu, K Cheng, Y Zhao, X Deng, D Sun. Nitrogen-containing carbon microspheres for supercapacitor electrodes. Electrochimica Acta, 2015, 158: 166–174
5 D C Guo, J Mi, G P Hao, W Dong, G Xiong, W C Li, A H Lu. Ionic liquid C16mimBF4 assisted synthesis of poly(benzoxazine-co-resol)-based hierarchically porous carbons with superior performance in supercapacitors. Energy & Environmental Science, 2013, 6(2): 652–659
6 L Wan, J Wang, L Xie, Y Sun, K Li. Nitrogen-enriched hierarchically porous carbons prepared from polybenzoxazine for high-performance supercapacitors. ACS Applied Materials & Interfaces, 2014, 6(17): 15583–15596
7 N P Wickramaratne, J Xu, M Wang, L Zhu, L Dai, M Jaroniec. Nitrogen enriched porous carbon spheres: Attractive materials for supercapacitor electrodes and CO2 adsorption. Chemistry of Materials, 2014, 26(9): 2820–2828
8 Y Wang, X Yan, M Tu, J Cheng, J Zhang. Resin-derived activated carbons with in-situ nitrogen doping and high specific surface area for high-performance supercapacitors. Materials Letters, 2017, 191: 178–181
9 F Liu, L Zeng, Y Chen, R Zhang, R Yang, J Pang, L Ding, H Liu, W Zhou. Ni-Co-N hybrid porous nanosheets on graphene paper for flexible and editable asymmetric all-solid-state supercapacitors. Nano Energy, 2019, 61: 18–26
10 D Zhu, J Jiang, D Sun, X Qian, Y Wang, L Li, Z Wang, X Chai, L Gan, M Liu. A general strategy to synthesize high-level N-doped porous carbons via Schiff-base chemistry for supercapacitors. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(26): 12334–12343
11 J Yan, D Zhu, Y Lv, W Xiong, M Liu, L Gan. Water-in-salt electrolyte ion-matched N/O codoped porous carbons for high-performance supercapacitors. Chinese Chemical Letters, 2019, 31(2): 579–582
12 Z Song, H Duan, D Zhu, Y Lv, W Xiong, T Cao, L Li, M Liu, L Gan. Ternary-doped carbon electrodes for advanced aqueous solid-state supercapacitors based on a “water-in-salt” gel electrolyte. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(26): 15801–15811
13 D Gueon, J H Moon. Nitrogen-doped carbon nanotube spherical particles for supercapacitor applications: Emulsion-assisted compact packing and capacitance enhancement. ACS Applied Materials & Interfaces, 2015, 7(36): 20083–20089
14 M Li, J Xue. Integrated synthesis of nitrogen-doped mesoporous carbon from melamine resins with superior performance in supercapacitors. Journal of Physical Chemistry C, 2014, 118(5): 2507–2517
15 K Zou, Y Deng, J Chen, Y Qian, Y Yang, Y Li, G Chen. Hierarchically porous nitrogen-doped carbon derived from the activation of agriculture waste by potassium hydroxide and urea for high-performance supercapacitors. Journal of Power Sources, 2018, 378: 579–588
16 B E Wilson, S He, K Buffington, S Rudisill, W H Smyrl, A Stein. Utilizing ionic liquids for controlled N-doping in hard-templated, mesoporous carbon electrodes for high-performance electrochemical double-layer capacitors. Journal of Power Sources, 2015, 298: 193–202
17 M Sevilla, A B Fuertes. Fabrication of porous carbon monoliths with a graphitic framework. Carbon, 2013, 56: 155–166
18 M Sevilla, J B Parra, A B Fuertes. Assessment of the role of micropore size and N-doping in CO2 capture by porous carbons. ACS Applied Materials & Interfaces, 2013, 5(13): 6360–6368
19 U Thubsuang, H Ishida, S Wongkasemjit, T Chaisuwan. Self-formation of 3D interconnected macroporous carbon xerogels derived from polybenzoxazine by selective solvent during the sol-gel process. Journal of Materials Science, 2014, 49(14): 4946–4961
20 U Thubsuang, H Ishida, S Wongkasemjit, T Chaisuwan. Advanced and economical ambient drying method for controlled mesoporepolybenzoxazine-based carbon xerogels: Effects of non-ionic and cationic surfactant on porous structure. Journal of Colloid and Interface Science, 2015, 459: 241–249
21 M Wang, J Wang, W Qiao, L Ling, D Long. Scalable preparation of nitrogen-enriched carbon microspheres for efficient CO2 capture. RSC Advances, 2014, 4(106): 61456–61464
22 M Tian, Y Sun, C Zhang, J Wang, W Qiao, L Ling, D Long. Enabling high-rate electrochemical flow capacitors based on mesoporous carbon microspheres suspension electrodes. Journal of Power Sources, 2017, 364: 182–190
23 U Thubsuang, H Ishida, S Wongkasemjit, T Chaisuwan. Novel template confinement derived from polybenzoxazine-based carbon xerogels for synthesis of ZSM-5 nanoparticles via microwave irradiation. Microporous and Mesoporous Materials, 2012, 156: 7–15
24 H Zhou, S Xu, H Su, M Wang, W Qiao, L Ling, D Long. Facile preparation and ultra-microporous structure of melamine-resorcinol-formaldehyde polymeric microspheres. Chemical Communications, 2013, 49(36): 3763–3765
25 L Liu, Z H Xie, Q F Deng, X X Hou, Z Y Yuan. One-pot carbonization enrichment of nitrogen in microporous carbon spheres for efficient CO2 capture. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(1): 418–425
26 D Zhang, J Zhao, C Feng, R Zhao, Y Sun, T Guan, B Han, N Tang, J Wang, K Li, J Qiao, J Zhang. Scalable synthesis of hierarchical macropore-rich activated carbon microspheres assembled by carbon nanoparticles for high rate performance supercapacitors. Journal of Power Sources, 2017, 342: 363–370
27 C M Lei, W L Yuan, H C Huang, S W Ho, C J Su. Synthesis and conductivity measurement of carbon spheres by catalytic CVD using non-magnetic metal complexes. Synthetic Metals, 2011, 161(15-16): 1590–1595
28 U Thubsuang, D Sukanan, S Sahasithiwat, S Wongkasemjit, T Chaisuwan. Highly sensitive room temperature organic vapor sensor based on polybenzoxazine-derived carbon aerogel thin film composite. Materials Science and Engineering B, 2015, 200: 67–77
29 T Takeichi, T Kano, T Agag. Synthesis and thermal cure of high molecular weight polybenzoxazine precursors and the properties of the thermosets. Polymer, 2005, 46(26): 12172–12180
30 S Brunauer, P H Emmett, E Teller. Adsorption of gases in multimolecular layers. Journal of the American Chemical Society, 1938, 60(2): 309–319
31 B C Lippens, J H de Boer. Study on pore systems in catalysts: V. The t method. Journal of Catalysis, 1965, 4(3): 319–323
32 D Wu, R Fu, M S Dresselhaus, G Dresselhaus. Fabrication and nano-structure control of carbon aerogels via a microemulsion-templated sol-gel polymerization method. Carbon, 2006, 44(4): 675–681
33 J Dunkers, H Ishida. Vibrational assignments of 3-alkyl-3,4-dihydro-6-methyl-2H-1,3-benzoxazines in the fingerprint region. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 1995, 51(6): 1061–1074
34 S Chen, J Wu, R Zhou, L Zuo, P Li, Y Song, L Wang. Porous carbon spheres doped with Fe3C as an anode for high-rate lithium-ion batteries. Electrochimica Acta, 2015, 180: 78–85
35 A A Alhwaige, T Agag, H Ishida, S Qutubuddin. Biobased chitosan/polybenzoxazine cross-linked films: Preparation in aqueous media and synergistic improvements in thermal and mechanical properties. Biomacromolecules, 2013, 14(6): 1806–1815
36 Y Zhao, M Liu, X Deng, L Miao, P K Tripathi, X Ma, D Zhu, Z Xu, Z Hao, L Gan. Nitrogen-functionalized microporous carbon nanoparticles for high performance supercapacitor electrode. Electrochimica Acta, 2015, 153: 448–455
37 N Manmuanpom, U Thubsuang, S T Dubas, T Wongkasemjit, T Chaisuwan. Enhanced CO2 capturing over ultra-microporous carbon with nitrogen-active species prepared using one-step carbonization of polybenzoxazine for a sustainable environment. Journal of Environmental Management, 2018, 223: 779–786
38 H Wang, H Peng, G Li, K Chen. Nitrogen-containing carbon/graphene composite nanosheets with excellent lithium storage performances. Chemical Engineering Journal, 2015, 275: 160–167
39 D Guo, R Xin, Y Wang, W Jiang, Q Gao, G Hu, M Fan. N-doped carbon with hierarchically micro- and mesoporous structure derived from sawdust for high performance supercapacitors. Microporous and Mesoporous Materials, 2019, 279: 323–333
40 A M Silvestre-Albero, J M Juarez-Galan, J Silvestre-Albero, F Rodriguez-Reinoso. Low-pressure hysteresis in adsorption: An artifact? Journal of Physical Chemistry C, 2012, 116(31): 16652–16655
41 M L Sekirifa, M Hadj-Mahammed, S Pallier, L Baameur, D Richard, A H Al-Dujaili. Preparation and characterization of an activated carbon from a date stones variety by physical activation with carbon dioxide. Journal of Analytical and Applied Pyrolysis, 2013, 99: 155–160
42 P Lorjai, S Wongkasemjit, T Chaisuwan, A M Jamieson. Significant enhancement of thermal stability in the non-oxidative thermal degradation of bisphenol-A/aniline based polybenzoxazine aerogel. Polymer Degradation & Stability, 2011, 96(4): 708–718
43 M C Liu, L B Kong, P Zhang, Y C Luo, L Kang. Porous wood carbon monolith for high-performance supercapacitors. Electrochimica Acta, 2012, 60: 443–448
Related articles from Frontiers Journals
[1] Shilei Ding, Zelong Jiang, Jing Gu, Hongliang Zhang, Jiajia Cai, Dongdong Wang. Carbon-coated lithium titanate: effect of carbon precursor addition processes on the electrochemical performance[J]. Front. Chem. Sci. Eng., 2021, 15(1): 148-155.
[2] Ammaru Ismaila, Xueli Chen, Xin Gao, Xiaolei Fan. Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure[J]. Front. Chem. Sci. Eng., 2021, 15(1): 60-71.
[3] Zishuai Liu, Yimin Zhang, Zilin Dai, Jing Huang, Cong Liu. Coextraction of vanadium and manganese from high-manganese containing vanadium wastewater by a solvent extraction-precipitation process[J]. Front. Chem. Sci. Eng., 2020, 14(5): 902-912.
[4] Jun Wei, Jianbo Zhao, Di Cai, Wenqiang Ren, Hui Cao, Tianwei Tan. Synthesis of micro/meso porous carbon for ultrahigh hydrogen adsorption using cross-linked polyaspartic acid[J]. Front. Chem. Sci. Eng., 2020, 14(5): 857-867.
[5] Yifei Wang, Shouying Huang, Xinsheng Teng, Hongyu Wang, Jian Wang, Qiao Zhao, Yue Wang, Xinbin Ma. Controllable Fe/HCS catalysts in the Fischer-Tropsch synthesis: Effects of crystallization time[J]. Front. Chem. Sci. Eng., 2020, 14(5): 802-812.
[6] Colin A. Scholes. Pilot plants of membrane technology in industry: Challenges and key learnings[J]. Front. Chem. Sci. Eng., 2020, 14(3): 305-316.
[7] Simon Roussanaly, Monika Vitvarova, Rahul Anantharaman, David Berstad, Brede Hagen, Jana Jakobsen, Vaclav Novotny, Geir Skaugen. Techno-economic comparison of three technologies for pre-combustion CO2 capture from a lignite-fired IGCC[J]. Front. Chem. Sci. Eng., 2020, 14(3): 436-452.
[8] Mahboube Ghahramaninezhad, Fatemeh Mohajer, Mahdi Niknam Shahrak. Improved CO2 capture performances of ZIF-90 through sequential reduction and lithiation reactions to form a hard/hard structure[J]. Front. Chem. Sci. Eng., 2020, 14(3): 425-435.
[9] Dawid P. Hanak, Vasilije Manovic. Linking renewables and fossil fuels with carbon capture via energy storage for a sustainable energy future[J]. Front. Chem. Sci. Eng., 2020, 14(3): 453-459.
[10] Viviana Maffeis, Lisa Moni, Daniele Di Stefano, Silvia Giordani, Renata Riva. Diversity-oriented synthesis of blue emissive nitrogen heterocycles and their conjugation with carbon nano-onions[J]. Front. Chem. Sci. Eng., 2020, 14(1): 76-89.
[11] Ying Yan, Peng Huang, Huiping Zhang. Preparation and characterization of novel carbon molecular sieve membrane/PSSF composite by pyrolysis method for toluene adsorption[J]. Front. Chem. Sci. Eng., 2019, 13(4): 772-783.
[12] Evelyn Chalmers, Yi Li, Xuqing Liu. Molecular tailoring to improve polypyrrole hydrogels’ stiffness and electrochemical energy storage capacity[J]. Front. Chem. Sci. Eng., 2019, 13(4): 684-694.
[13] Sidra Rama, Yan Zhang, Fideline Tchuenbou-Magaia, Yulong Ding, Yongliang Li. Encapsulation of 2-amino-2-methyl-1-propanol with tetraethyl orthosilicate for CO2 capture[J]. Front. Chem. Sci. Eng., 2019, 13(4): 672-683.
[14] Fenghua Liu, Yijian Lai, Binyuan Zhao, Robert Bradley, Weiping Wu. Photothermal materials for efficient solar powered steam generation[J]. Front. Chem. Sci. Eng., 2019, 13(4): 636-653.
[15] Yingying Zhao, Mengfan Wu, Zhiyong Ji, Yuanyuan Wang, Jiale Li, Jianlu Liu, Junsheng Yuan. A combination process of mineral carbonation with SO2 disposal for simulated flue gas by magnesia-added seawater[J]. Front. Chem. Sci. Eng., 2019, 13(4): 832-844.
Full text