Abstract
Structural defects in graphene directly influence its electronic structure and can lead to the development of unique properties. However, the introduction of defects into ordered mesoporous graphitic carbons has yet to be demonstrated. Herein, defects were successfully introduced into the graphitic carbon lattice of well-ordered hexagonal mesoporous carbons via a block copolymer soft-template method and high-temperature carbonization. Small-angle X-ray scattering, scanning electron microscopy, and nitrogen adsorption measurements revealed that well-ordered ~4 nm cylindrical mesoporous structures with high surface areas (532 m2g−1) and good mesoporosity were maintained after high-temperature carbonization up to 1500 °C and mechanical milling. Raman and CHN elemental analyses suggested that defects were introduced into the graphitic carbon lattice through surface reconstruction induced by N-atom removal during heat treatment. The obtained robust and well-ordered N-containing mesoporous carbons with deliberately introduced defects are considered promising materials for electrochemical reactions and as catalyst supports.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Banhart F, Kotakoski J, Krasheninnikov AV. Structural defects in graphene. ACS Nano. 2011;5:26–41.
Zhao H, Sun C, Jin Z, Wang D-W, Yan X, Chen Z, Zhu G, Yao X. Carbon for the oxygen reduction reaction: a defect mechanism. J Mater Chem A. 2015;3:11736–9.
Jia Y, Zhang L, Du A, Gao G, Chen J, Yan X, Brown CL, Yao X. Defect graphene as a trifunctional catalyst for electrochemical reactions. Adv Mater. 2016;28:9532–8.
Tao H, Gao Y, Talreja N, Guo F, Texter J, Yan C, Sun Z. Two-dimensional nanosheets for electrocatalysis in energy generation and conversion. J Mater Chem A. 2017;5:7257–84.
Cheng I, Hou Yi, Hu Y, Narita A, Müllen, K. Diels–Alder polymerization: a versatile synthetic method toward functional polyphenylenes, ladder polymers and graphene nanoribbons. Polym J. 2018;50:3-20.
Sun H-S, Chiu Y-C, Chen W-C. Renewable polymeric materials for electronic applications. Polym J. 2016;49:61–73.
Mohammadi N, Adeh NB, Najafi M. Synthesis and characterization of highly defective mesoporous carbon and its potential use in electrochemical sensors. RSC Adv. 2016;6:33419–25.
Goettmann F, Fischer A, Antonietti M, Thomas A. Chemical synthesis of mesoporous carbon nitrides using hard templates and their use as a metal-free catalyst for friedel–crafts reaction of benzene. Angew Chem Int Ed. 2006;45:4467–71.
Lin T, Chen I-W, Liu F, Yang C, Bi H, Xu F, Huang F. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science. 2015;350:1508–13.
Liu R, Wu D, Feng X, Müllen K. Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem. 2010;122:2619–23.
Wan K, Long GF, Liu MY, Du L, Liang ZX, Tsiakaras P. Nitrogen-doped ordered mesoporous carbon: synthesis and active sites for electrocatalysis of oxygen reduction reaction. Appl Catal B Environ. 2015;165:566–71.
Wang H, Ding J, Zhang J, Wang C, Yang W, Ren H, Kong A. Fluorine and nitrogen co-doped ordered mesoporous carbon as a metal-free electrocatalyst for oxygen reduction reaction. RSC Adv. 2016;6:79928–33.
Wang X, He Z, Shi Y, Li B. Nitrogen-doped ordered mesoporous carbon as metal-free catalyst for power generation in single chamber microbial fuel cells. J Electrochem Soc. 2017;164:F620–7.
Wang J, Xin HL, Wang D. Recent progress on mesoporous carbon materials for advanced energy conversion and storage. Part Syst Charact. 2014;31:515–39.
Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater. 2008;7:845–54.
Xin W, Song Y. Mesoporous carbons: recent advances in synthesis and typical applications. RSC Adv. 2015;5:83239–85.
Liang C, Li Z, Dai S. Mesoporous carbon materials: synthesis and modification. Angew Chem Int Ed. 2008;47:3696–717.
Fang Y, Lv Y, Che R, Wu H, Zhang X, Gu D, Zheng G, Zhao D. Two-dimensional mesoporous carbon nanosheets and their derived graphene nanosheets: synthesis and efficient lithium ion storage. J Am Chem Soc. 2013;135:1524–30.
Wang X, Liang C, Dai S. Facile synthesis of ordered mesoporous carbons with high thermal stability by self-assembly of resorcinol-formaldehyde and block copolymers under highly acidic conditions. Langmuir. 2008;24:7500–5.
Yu J, Guo M, Muhammad F, Wang A, Yu G, Ma H, Zhu G. Simple fabrication of an ordered nitrogen-doped mesoporous carbon with resorcinol-melamine-formaldehyde resin. Microporous Mesoporous Mater. 2014;190:117–27.
Cai T, Zhou M, Ren D, Han G, Guan S. Highly ordered mesoporous phenol-formaldehyde carbon as supercapacitor electrode material. J Power Sources. 2013;231:197–202.
Wei J, Zhou D, Sun Z, Deng Y, Xia Y, Zhao D. A controllable synthesis of rich nitrogen-doped ordered mesoporous carbon for CO2 capture and supercapacitors. Adv Funct Mater. 2013;23:2322–8.
Meng Y, Gu D, Zhang F, Shi Y, Cheng L, Feng D, Wu Z, Chen Z, Wan Y, Stein A, Zhao D. A family of highly ordered mesoporous polymer resin and carbon structures from organic-organic self-assembly. Chem Mater. 2006;18:4447–64.
Liu Y, Ohnishi K, Sugimoto S, Okuhara K, Maeda R, Nabae Y, Kakimoto M, Wang X, Hayakawa T. Well-ordered mesoporous polymers and carbons based on imide-incorporated soft materials. Polym Chem. 2014;5:6452–60.
Hsueh H-Y, Yao C-T, Ho R-M. Well-ordered nanohybrids and nanoporous materials from gyroid block copolymer templates. Chem Soc Rev. 2015;44:1974–2018.
Mun Y, Shim J, Kim K, Han JW, Kim S-K, Ye Y, Hwang J, Lee S, Jang J, Kim Y-T, Lee J. Direct access to aggregation-free and small intermetallic nanoparticles in ordered, large-pore mesoporous carbon for an electrocatalyst. RSC Adv. 2016;6:88255–64.
Tang J, Liu J, Li C, Li Y, Tade MO, Dai S, Yamauchi Y. Synthesis of nitrogen-doped mesoporous carbon spheres with extra-largepores through assembly of diblock copolymer micelles. Angew Chem Int Ed. 2015;54:588–93.
Jones BH, Lodge TP. Nanocasting nanoporous inorganic and organic materials from polymeric bicontinuous microemulsion templates. Polym J. 2012;44:131–46.
Wiesenauer BR, Gin DL. Nanoporous polymer materials based on self-organized, bicontinuous cubic lyotropic liquid crystal assemblies and their applications. Polym J. 2012;4415:461–8.
Sato K, Ishii K, Oaki Y, Nakanishi K, Imai H. Polymer-assisted shapeable synthesis of porous frameworks consisting of silica nanoparticles with mechanical property tuning. Polym J. 2017;49:825-30.
Sevilla M, Yu L, Fellinger TP, Fuertes AB, Titirici M-M. Polypyrrole-derived mesoporous nitrogen-doped carbons with intrinsic catalytic activity in the oxygen reduction reaction. RSC Adv. 2013;3:9904.
Wang K, Zhang J, Xia W, Zou R, Guo J, Gao Z, Yan W, Guo S, Xu Q. A dual templating route to three-dimensionally ordered mesoporous carbon nanonetworks: tuning the mesopore type for electrochemical performance optimization. J Mater Chem A. 2015;3:18867–73.
Nabae Y, Nagata S, Ohnishi K, Liu Y, Sheng L, Wang X, Hayakawa T. Block copolymer templated carbonization of nitrogen containing polymer to create fine and mesoporous carbon for oxygen reduction catalyst. J Polym Sci Part A Polym Chem. 2017;55:464–70.
Liang Y, Fu R, Wu D. Reactive template-induced self-assembly to ordered mesoporous polymeric and carbonaceous materials. ACS Nano. 2013;7:1748–54.
Sharifi T, Hu G, Jia X, Wågberg T. Formation of active sites for oxygen reduction reactions by transformation of nitrogen functionalities in nitrogen-doped carbon nanotubes. ACS Nano. 2012;6:8904–12.
Vinu A. Two-dimensional hexagonally-ordered mesoporous carbon nitrides with tunable pore diameter, surface area and nitrogen content. Adv Funct Mater. 2008;18:816–27.
Acknowledgements
We are grateful to Ryohei Kikuchi of the Tokyo Institute of Technology, Ookayama, Materials Analysis Division, and Prof. Yuji Wada of the Tokyo Institute of Technology, Department of Chemical Science and Engineering, for assistance in the SEM measurements. We also would like to thank the Suzukakedai Materials Analysis Division, Technical Department, Tokyo Institute of Technology, for the CHN analysis. This work was partially funded by the Japan Science and Technology Agency (JST), the Precursory Research for Embryonic Science and Technology (PRESTO) on the Molecular Technology and Creation of New Functions.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Rights and permissions
About this article
Cite this article
Gao, L., Chandra, A., Nabae, Y. et al. Inducing defects in ordered mesoporous carbons via the block copolymer-templated high-temperature carbonization of nitrogen-containing polymeric precursors. Polym J 50, 389–396 (2018). https://doi.org/10.1038/s41428-018-0023-0
Received:
Revised:
Accepted:
Published:
Version of record:
Issue date:
DOI: https://doi.org/10.1038/s41428-018-0023-0
This article is cited by
-
Ordered porous carbon preparation by hard templating approach for hydrogen adsorption application
Biomass Conversion and Biorefinery (2024)
