Please wait a minute...
Shopping Cart Email List Chinese
Advanced Search Fig/Tab
Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

Featured Articles  |  Most Downloaded  |  Most Reading
Online Submission Subscribe to Our RSS Content Feed
Front. Chem. Sci. Eng.    2020, Vol. 14 Issue (5) : 857-867    https://doi.org/10.1007/s11705-019-1880-6
RESEARCH ARTICLE
Synthesis of micro/meso porous carbon for ultrahigh hydrogen adsorption using cross-linked polyaspartic acid
Jun Wei1, Jianbo Zhao1,2, Di Cai1(), Wenqiang Ren3, Hui Cao1(), Tianwei Tan1
1. National?Energy?Research and Development?Center?for?Biorefinery, Beijing University of Chemical Technology, Beijing 100029, China
2. Engineering Laboratory of Chemical Resources Utilization in South Xinjiang of Xinjiang Production and Construction Corps, College of Life Sciences, Tarim University, Alar 843300, China
3. Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, China
 Download: PDF(2164 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

In addition to the specific surface area, surface topography and characteristics such as the pore size, pore size distribution, and micro/mesopores ratio are factors that determine the performance of porous carbons (PCs) in the fields of energy, catalysis, and adsorption. Based on the mechanism of weight loss of polyaspartic acid at high temperatures, this study provided a new method for adjusting the surface morphology of PCs by changing the cross-linking ratio of the precursor, where cross-linked polyaspartic acid was used as precursor without additional activating agents. N2 adsorption analysis indicated that the specific surface area of the obtained PCs was as high as 1458 m2·g–1, of which 1200 m2·g–1 was the contribution of the microporous area and the highest pore volume was 1.13 cm3·g–1, of which the micropore volume was 0.636 cm3·g–1. The thermogravimetric analysis results of the precursor, and also the scanning electron microscopy and Brunauer–Emmet–Teller analysis results of the carbonization product confirmed that the prepared PCs presented multilevel pore structure, and the diameters of most pores were 0.78 and 3.97 nm; moreover, the pore size distribution was relatively uniform. This conferred the PCs the ultrahigh hydrogen adsorption capacity of up to 4.52 wt-% at 77 K and 1.13 bar, in addition to their great energy storage and catalytic potential.
Keywords porous carbon      multilevel pores      polyaspartic acid      cross-linking      hydrogen adsorption     
Corresponding Author(s): Di Cai,Hui Cao   
Online First Date: 15 January 2020    Issue Date: 25 May 2020
 Cite this article:   
Jun Wei,Jianbo Zhao,Di Cai, et al. 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.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1880-6
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I5/857
Fig.1  Flowchart of CroPASP and PCs production.
Fig.2  Swelling of CroPASP with different cross-linking ratios.
Fig.3  TGA of CroPASP samples with different cross-linking ratios.
Fig.4  SEM images of PCs. Here, C-CroPASP40, C-CroPASP30, C-CroPASP20 and C-CroPASP15 are carbonized CroPASP specimens with different cross-linking ratios (40, 30, 20 and 15, respectively); C-PASP is carbonized CroPASP.
Fig.5  HRTEM images of PCs. Here, C-CroPASP40, C-CroPASP30, C-CroPASP20 and C-CroPASP15 are carbonized CoPASP specimens with different cross-linking ratios (40, 30, 20 and 15, respectively).
Fig.6  (a) XRD patterns; (b) Raman spectra; (c) ratio of intensities of D/G peaks (ID/IG) and full width at half maximum (FWHM) of PCs. Here, C-CroPASP40, C-CroPASP30, C-CroPASP20 and C-CroPASP15 are carbonized CroPASP specimens with different cross-linking ratios (40, 30, 20 and 15, respectively), and C-PASP is carbonized CroPASP.
Fig.7  XPS profiles of PCs. Here, C-CroPASP40, C-CroPASP30, C-CroPASP20 and C-CroPASP15 are carbonized CroPASP specimens with different cross-linking ratios (40, 30, 20 and 15, respectively), and C-PASP is carbonized CroPASP.
Sample SBET b)
/(m2?g?1)		 Smicro c)
/(m2?g?1)		 VTotal d)
/(cm3?g?1)		 Vmicroe)
/(cm3?g?1)		 Elemental content/wt-% f) Elemental content/wt-% g)
C O N C O N
C-CroPASP40 662 542 0.468 0.292 90.30 6.32 3.37 88.42 8.12 3.46
C-CroPASP30 1110 899 0.781 0.485 90.52 7.74 1.75 89.11 8.87 2.02
C-CroPASP20 1458 1200 1.130 0.636 89.95 7.58 2.47 86.02 11.29 2.69
C-CroPASP15 1122 955 0.769 0.515 89.69 7.08 3.23 85.38 13.68 2.94
C-PASP 952 787 0.610 0.42 87.23 11.33 1.44 83.77 14.31 1.92
Tab.1  Pore properties and elemental content of PCs a)
Fig.8  (a) N2 adsorption–desorption isotherms, and (b)?(d) pore size distribution curves of PCs. Here C-CroPASP40, C-CroPASP30, C-CroPASP20 and C-CroPASP15 are carbonized CroPASP specimens with different cross-linking ratios (40, 30, 20 and 15, respectively), and C-PASP is carbonized CroPASP.
Fig.9  Hydrogen adsorption curves of PCs at 77.3 K and pressure as high as 1.13 bar. Hydrogen adsorption properties of commercial active carbon samples from Aladdin (China) and Sigma-Aldrich (Germany) were also included for comparison. Here, C-CroPASP40, C-CroPASP30, C-CroPASP20 and C-CroPASP15 are carbonized CroPASP specimens with different cross-linking ratios (40, 30, 20 and 15, respectively), and C-PASP is carbonized CroPASP.
Sample H2 uptake
/wt-%		 SBET
/(m2?g?1)		 VTotal
/(cm3?g?1)		 Adsorption conditions Ref.
C-CroPASP15 4.33 1122 0.769 77 K, 1.13 bar
C-CroPASP20 4.52 1458 1.130
C-CroPASP30 3.73 1110 0.781
C-CroPASP40 2.93 662 0.468
NAC-1.5-600 2.96 1317 0.64 77 K, 1.0 bar [39]
MDC-1 3.25 3174 4.06 77 K, 1.0 bar [13]
CHCPB-K-700 3.25 3101 1.84 77.3 K, 1.13 bar [2]
RFC_C240 3.16 3540 1.99 77 K, 1.0 bar [40]
RFC_C380 3.26 4079 2.56
PFC_C120 3.05 3283 1.48
CAC0 2.42 3148 1.5 77 K, 1.0 bar [41]
CAC1 2.85 2988 1.36
CAC7 2.66 3530 1.95
Ch700/700/3 2.9 3066 1.38 77 K, 1.0 bar [42]
Ch700/800/3 2.95 2481 0.95
CAC1 2.85 3009 1.44 77 K, 1.0 bar [43]
CAC4 3.21 3708 2
Tab.2  H2 adsorption capacity of C-CroPASPs compared with data reported in the literaturea)
1 L Shao, S Wang, M Liu, J Huang, Y Liu. Triazine-based hyper-cross-linked polymers derived porous carbons for CO2 capture. Chemical Engineering Journal, 2018, 339: 509–518
2 C Zhang, R Kong, X Wang, Y Xu, F Wang, W Ren, Y Wang, F Su, J Jiang. Porous carbons derived from hypercross-linked porous polymers for gas adsorption and energy storage. Carbon, 2017, 114: 608–618
3 T S Blankenship, N Balahmar, R Mokaya. Oxygen-rich microporous carbons with exceptional hydrogen storage capacity. Nature Communications, 2017, 8: 1545
4 M Sevilla, R Mokaya, A B Fuertes. Ultrahigh surface area polypyrrole based carbons with superior performance for hydrogen storage. Energy & Environmental Science, 2011, 4: 2930–2936
5 Y Xia, G S Walker, D M Grant, R Mokaya. Hydrogen storage in high surface area carbons: Experimental demonstration of the effects of nitrogen doping. Journal of the American Chemical Society, 2009, 131: 16493–16499
6 X B Zhao, B Xiao, A J Fletcher, K M Thomas. Hydrogen adsorption on functionalized nanoporous activated carbons. Journal of Physical Chemistry B, 2005, 109: 8880–8888
7 Z Yang, Y Xia, X Sun, R Mokaya. Preparation and hydrogen storage properties of zeolite-templated carbon materials nanocast via chemical vapor deposition: Effect of the xeolite template and nitrogen doping. Journal of Physical Chemistry B, 2006, 110: 18424–18431
8 K Nanaji, H E Mohan, V B Sarada, U V Varadaraju, N T Rao, S Anandan. One step synthesized hierarchical spherical porous carbon as an efficient electrode material for lithium ion battery. Materials Letters, 2019, 237: 156–160
9 J Wei, C Ding, P Zhang, H Ding, X Niu, Y Ma, C Li, Y Wang, H Xiong. Robust negative electrode materials derived from carbon dots and porous hydrogels for high-performance hybrid supercapacitors. Advanced Materials, 2019, 31(5): e1806197
10 X Yang, K Li, D Cheng, W Pang, J Lv, X Chen, H Zang, X Wu, H Tan, Y Wang, et al. Nitrogen-doped porous carbon: Highly efficient trifunctional electrocatalyst for oxygen reversible catalysis and nitrogen reduction reaction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(17): 7762–7769
11 Y Cao, S Mao. Li Mg, Chen Y, Wang Y. Metal/porous carbon composites for heterogeneous catalysis: Old catalysts with improved performance promoted by N-doping. ACS Catalysis, 2017, 7(12): 8090–8112
12 Z Yang, Z Liu, H Zhang, B Yu, Y Zhao, H Wang, G Ji, Y Chen, X Liu, Z Liu. N-Doped porous carbon nanotubes: Synthesis and application in catalysis. Chemical Communications, 2016, 53(5): 929–932
13 S J Yang, T Kim, J H Im, Y S Kim, K Lee, H Jung. Park C R. MOF-derived hierarchically porous carbon with exceptional porosity and hydrogen storage capacity. Chemistry of Materials, 2012, 24(3): 464–470
14 L Zhang, T You, T Zhou, X Zhou, F Xu. Interconnected hierarchical porous carbon from lignin-derived byproducts of bioethanol production for ultra-high performance supercapacitors. ACS Applied Materials & Interfaces, 2016, 8: 13918–13925
15 M Xu, D Li, Y Yan, T Guo, H Pang, H Xue. Porous high specific surface area-activated carbon with co-doping N, S and P for high-performance supercapacitors. RSC Advances, 2017, 7: 43780–43788
16 J Cui, Y Xi, S Chen, D Li, X She, J Sun, W Han, D Yang, S Guo. Prolifera-green-tide as sustainable source for carbonaceous aerogels with hierarchical pore to achieve multiple energy storage. Advanced Functional Materials, 2016, 26(46): 8487–8495
17 P Xiao, Q Meng, L Zhao, J Li, Z Wei, B Han. Biomass-derived flexible porous carbon materials and their applications in supercapacitor and gas adsorption. Materials & Design, 2017, 129: 164–172
18 J Cao, C Zhu, Y Aoki, H Habazaki. Starch-derived hierarchical porous carbon with controlled porosity for high performance supercapacitors. ACS Sustainable Chemistry & Engineering, 2018, 6(6): 7292–7303
19 Y Zhong, T Shi, Y Huang, S Cheng, G Liao, Z Tang. One-step synthesis of porous carbon derived from starch for all-carbon binder-free high-rate supercapacitor. Electrochimica Acta, 2018, 269: 676–685
20 M C Ghimbeu, A V Luchnikov. Hierarchical porous nitrogen-doped carbon beads derived from biosourced chitosan polymer. Microporous and Mesoporous Materials, 2018, 263: 42–52
21 P Song, X Shen, W He, L Kong, X He, Z Ji, A Yuan, G Zhu, N Li. Protein-derived nitrogen-doped hierarchically porous carbon as electrode material for supercapacitors. Journal of Materials Science Materials in Electronics, 2018, 29(14): 12206–12215
22 S M Alatalo, K Qiu, K Preuss, A Marinovic, M Sevilla, M Sillanpää, X Guo, M Titirici. Soy protein directed hydrothermal synthesis of porous carbon aerogels for electrocatalytic oxygen reduction. Carbon, 2016, 96: 622–630
23 M Demir, B Ashourirad, H J Mugumya, K S Saraswat, M H El-Kaderi, B R Gupt. Nitrogen and oxygen dual-doped porous carbons prepared from pea protein as electrode materials for high performance supercapacitors. International Journal of Hydrogen Energy, 2018, 43(40): 18549–18558
24 J Zhang, Y Cai, Q Zhong, D Lai, J Yao. Porous Nitrogen-doped carbon derived from silk fibroin protein encapsulating sulfur as a superior cathode material for high-performance lithium-sulfur batteries. Nanoscale, 2015, 7(42): 17791–17797
25 Y Zhao, H Su, L Fang, T Tan. Superabsorbent hydrogels from poly (aspartic acid) with salt-, temperature- and pH-responsiveness properties. Polymer, 2005, 46: 5368–5376
26 H Cao, X Ma, S Sun, H Su, T Tan. A new photocrosslinkable hydrogel based on a derivative of polyaspartic acid for the controlled release of ketoprofen. Polymer Bulletin, 2010, 64: 623–632
27 H Cheng, Y Li, X Zeng, Y X Sun, X Z Zhang, R X Zhuo. Protamine sulfate/poly(l-aspartic acid) polyionic complexes self-assembled via electrostatic attractions for combined delivery of drug and gene. Biomaterials, 2009, 30: 1246–1253
28 H Meng, X Zhang, Q Chen, J Wei, Y Wang, A Dong, H Yang, T Tan, H Cao. Preparation of poly (aspartic acid) superabsorbent hydrogels by solvent-free processes. Journal of Polymer Engineering, 2015, 35(7): 647–655
29 S L Lim, W N H Tang, C W Ooi, E Chan, B T Tey. Rapid swelling and deswelling of semi-interpenetrating network poly (acrylic acid)/poly(aspartic acid) hydrogels prepared by freezing polymerization. Journal of Applied Polymer Science, 2016, 133(24): e43515
30 M Edwin, P Sadanand, R James. Microwave assisted synthesis of xanthan gum-cl-poly (acrylic acid) based-reduced graphene oxide hydrogel composite for adsorption of methylene blue and methyl violet from aqueous solution. International Journal of Biological Macromolecules, 2018, 119: 255–269
31 J Wang, I Senkovska, S Kaskel, Q Liu. Chemically activated fungi-based porous carbons for hydrogen storage. Carbon, 2014, 75: 372–380
32 J Tian, H Zhang, Z Liu, G Qin, Z Li. One-step synthesis of 3D sulfur-doped porous carbon with multilevel pore structure for high-rate supercapacitors. International Journal of Hydrogen Energy, 2018, 43(3): 1596–1605
33 G Srinivas, J Burress, T Yildirim. Graphene oxide derived carbons (GODCs): Synthesis and gas adsorption properties. Energy & Environmental Science, 2012, 5: 6453–6459
34 H Wang, X Sun, Z Liu, Z Lei. Creation of nanopores on graphene planes with MgO template for preparing high-performance supercapacitor electrodes. Nanoscale, 2014, 6: 6577–6584
35 X Yang, M Yu, Y Zhao, C Zhang, X Wang, J X Jiang. Remarkable gas adsorption by carbonized nitrogen-rich hypercross-linked porous organic polymers. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2: 15139–15145
36 K S W Sing, D H Everett, R A W Haul, L Moscou, R A Pierotti, J Rouquerol, T Siemieniewska. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure and Applied Chemistry, 1985, 57: 603–619
37 M Sevilla, R Mokaya. Energy storage applications of activated carbons: Supercapacitors and hydrogen storage. Energy & Environmental Science, 2014, 7: 1250–1280
38 P A Kobielska, R Telford, J Rowlandson, M Tian, Z Shahin, A Demessence, V P Ting, S Nayak. Polynuclear complexes as precursor templates for hierarchical microporous graphitic carbon: An unusual approach. ACS Applied Materials & Interfaces, 2018, 10: 25967–25971
39 G Sethia, A Sayari. Activated carbon with optimum pore size distribution for hydrogen storage. Carbon, 2016, 99: 289–294
40 H S Kim, M S Kang, W C Yoo. Highly enhanced gas sorption capacities of N-doped porous carbon spheres by hot NH3 and CO2 treatments. Journal of Physical Chemistry C, 2015, 119(51): 28512–28522
41 C Zhang, Z Geng, M Cai, J Zhang, X Liu, H Xin, J Ma. Microstructure regulation of super activated carbon from biomass source corncob with enhanced hydrogen uptake. International Journal of Hydrogen Energy, 2013, 38(22): 9243–9250
42 I Wrobel-Iwaniec, N Díez, G Gryglewicz. Chitosan-based highly activated carbons for hydrogen storage. International Journal of Hydrogen Energy, 2015, 40: 5788–5796
43 X Liu, C Zhang, Z Geng, M Cai. High-pressure hydrogen storage and optimizing fabrication of corncob-derived activated carbon. Microporous and Mesoporous Materials, 2014, 194: 60–65
[1] 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.
[2] Di Lu, Ran Tao, Zheng Wang. Carbon-based materials for photodynamic therapy: A mini-review[J]. Front. Chem. Sci. Eng., 2019, 13(2): 310-323.
[3] Tao Zhang, Tewodros Asefa. Copper nanoparticles/polyaniline-derived mesoporous carbon electrocatalysts for hydrazine oxidation[J]. Front. Chem. Sci. Eng., 2018, 12(3): 329-338.
[4] Chao Zhang, Chenbao Lu, Shuai Bi, Yang Hou, Fan Zhang, Ming Cai, Yafei He, Silvia Paasch, Xinliang Feng, Eike Brunner, Xiaodong Zhuang. S-enriched porous polymer derived N-doped porous carbons for electrochemical energy storage and conversion[J]. Front. Chem. Sci. Eng., 2018, 12(3): 346-357.
[5] LIU Zhenfa, WANG Yanji, GAO Yuhua, ZHANG Lihui. Synergistic scale inhibition of polyaspartic acid composite with magnetic field[J]. Front. Chem. Sci. Eng., 2007, 1(3): 261-265.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed