One- and two-dimensional carbon nanomaterials are attracting considerable attention because of their extraordinary electrical, mechanical and thermal properties, which could lead to a range of important potential applications. Synthetic processes associated with making these materials can be quite complex and also consume large amounts of energy, so a major challenge is to develop simple and efficient methods to produce them. Here, we present a self-templated, catalyst-free strategy for the synthesis of one-dimensional carbon nanorods by morphology-preserved thermal transformation of rod-shaped metal–organic frameworks. The as-synthesized non-hollow (solid) carbon nanorods can be transformed into two- to six-layered graphene nanoribbons through sonochemical treatment followed by chemical activation. The performance of these metal–organic framework-derived carbon nanorods and graphene nanoribbons in supercapacitor electrodes demonstrates that this synthetic approach can produce functionally useful materials. Moreover, this approach is readily scalable and could be used to produce carbon nanorods and graphene nanoribbons on industrial levels.
Subscribe to Journal
Get full journal access for 1 year
only $14.08 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Novoselov, K. S. et al.. A roadmap for graphene. Nature 490, 192–200 (2012).
Dai, H. Carbon nanotubes, from synthesis to integration and properties. Acc. Chem. Res. 35, 1035–1044 (2002).
Zhu, Y. et al.. Carbon-based supercapacitors produced by activation of graphene. Science 332, 1537–1541 (2011).
De Jong, K. P. & Geus, J. W. Carbon nanofibers: catalytic synthesis and applications. Catal. Rev. Sci. Eng. 42, 481–510 (2000).
Gadipelli, S. & Guo, Z. X. Graphene-based materials: synthesis and gas sorption, storage and separation. Prog. Mater. Sci. 69, 1–60 (2015).
Arico, A. S., Bruce, P., Scrosati, B., Tarascon, J.-M. & van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nature Mater. 4, 366–377 (2005).
Salunkhe, R. R. et al.. Asymmetric supercapacitors using 3D nanoporous carbon and cobalt oxide electrodes synthesized from a single metal–organic framework. ACS Nano 9, 6288–6296 (2015).
Yang, S., Bachman, R. E., Feng, X. & Müllen, K. Use of organic precursors and graphenes in the controlled synthesis of carbon-containing nanomaterials for energy storage and conversion. Acc. Chem. Res. 46, 116–128 (2013).
Kumar, M. & Ando, Y. Chemical vapor deposition of carbon nanotubes: a review on growth mechanism and mass production. J. Nanosci. Nanotechnol. 10, 3739–3758 (2010).
Kosynkin, D. V. et al.. Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons. Nature 458, 872–876 (2009).
Shinde, D. B., Debgupta, J., Kushwaha, A., Aslam, M. & Pillai, V. K. Electrochemical unzipping of multi-walled carbon nanotubes for facile synthesis of high-quality graphene nanoribbons. J. Am. Chem. Soc. 133, 4168–4171 (2011).
Ma, L., Wang, J. & Ding, F. Recent progress and challenges in graphene nanoribbon synthesis. ChemPhysChem 14, 47–54 (2013).
Terrones, M. et al.. Graphene and graphite nanoribbons: morphology, properties, synthesis, defects and applications. Nano Today 5, 351–372 (2010).
Dutta, S. & Pati, S. K. Novel properties of graphene nanoribbons: a review. J. Mater. Chem. 20, 8207–8223 (2010).
Eddaoudi, M. et al.. Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal−organic carboxylate frameworks. Acc. Chem. Res. 34, 319–330 (2001).
Slater, A. G. & Cooper, A. I. Function-led design of new porous materials. Science 348, aaa8075 (2015).
Yang, S. et al.. Selectivity and direct visualisation of carbon dioxide and sulphur dioxide in a decorated porous host. Nature Chem. 4, 887–894 (2012).
Liu, B., Shioyama, H., Akita, T. & Xu, Q. Metal−organic framework as a template for porous carbon synthesis. J. Am. Chem. Soc. 130, 5390–5391 (2008).
Tang, J. et al.. Thermal conversion of core–shell metal−organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon. J. Am. Chem. Soc. 137, 1572–1580 (2015).
Hao, G. P. et al. Unusual ultra-hydrophilic, porous carbon cuboids for atmospheric-water capture. Angew. Chem. Int. Ed. 54, 1941–1945 (2015).
Das, R., Pachfule, P., Banerjee, R. & Poddar, P. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides. Nanoscale 4, 591–599 (2012).
Xia, W., Mahmood, A., Zou, R. & Xu, Q. Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion. Energy Environ. Sci. 8, 1837–1866 (2015).
Sun, J.-K. & Xu, Q. Functional materials derived from open framework templates/precursors: synthesis and applications. Energy Environ. Sci. 7, 2071–2100 (2014).
Luo, J., Jang, H. D. & Huang, J. Effect of sheet morphology on the scalability of graphene-based ultracapacitors. ACS Nano. 7, 1464–1471 (2013).
Salunkhe, R. R. et al.. Fabrication of symmetric supercapacitors based on MOF-derived nanoporous carbons. J. Mater. Chem. A 2, 19848–19854 (2014).
Xu, X., Cao, R., Jeong, S. & Cho, J. Spindle-like mesoporous α-Fe2O3 anode material prepared from MOF template for high-rate lithium batteries. Nano Lett. 12, 4988–4991 (2012).
Pachfule, P., Biswal, B. P. & Banerjee, R. Control of porosity by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template for porous carbon synthesis. Chem. Eur. J. 18, 11399–11408 (2012).
Rowsell, J. L. C. & Yaghi, O. M. Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal−organic frameworks. J. Am. Chem. Soc. 128, 1304–1315 (2006).
Ma, J. L., Wong-Foy, A. G. & Matzger, A. J. The role of modulators in controlling layer spacings in a tritopic linker based zirconium 2D microporous coordination polymer. Inorg. Chem. 54, 4591–4593 (2015).
McGuire, C. V. & Forgan, R. S. The surface chemistry of metal–organic frameworks. Chem. Commun. 51, 5199–5217 (2015).
Li, P. et al.. Synthesis of nanocrystals of Zr-based metal–organic frameworks with csq-net: significant enhancement in the degradation of a nerve agent simulant. Chem. Commun. 51, 10925–10928 (2015).
Yu, D., Yazaydin, A. O., Lane, J. R., Dietzel, P. D. C. & Snurr, R. Q. A combined experimental and quantum chemical study of CO2 adsorption in the metal−organic framework CPO-27 with different metals. Chem. Sci. 4, 3544–3556 (2013).
Tranchemontagne, D. J., Hunt, J. R. & Yaghi, O. M. Room temperature synthesis of metal–organic frameworks: MOF-5, MOF-74, MOF-177, MOF-199, and IRMOF-0. Tetrahedron 64, 8553–8557 (2008).
Yue, Y. et al.. Template-free synthesis of hierarchical porous metal–organic frameworks. J. Am. Chem. Soc. 135, 9572–9575 (2013).
Coleman, J. N. Liquid-phase exfoliation of nanotubes and graphene. Adv. Funct. Mater. 19, 3680–3695 (2009).
Jiao, L., Wang, X., Diankov, G., Wang, H. & Dai, H. Facile synthesis of high-quality graphene nanoribbons. Nature Nanotech. 5, 321–325 (2010).
Xu, H. & Suslick, K. S. Sonochemical preparation of functionalized graphenes. J. Am. Chem. Soc. 133, 9148–9151 (2011).
Wang, I. & Kaskel, S. KOH activation of carbon-based materials for energy storage. J. Mater. Chem. 22, 23710–23725 (2012).
Lyon, L. A. Raman spectroscopy. Anal. Chem. 70, 341R–361R (1998).
Jiao, L., Zhang, L., Wang, X., Diankov, G. & Dai, H. Narrow graphene nanoribbons from carbon nanotubes. Nature 458, 877–880 (2009).
Zhang, Z., Sun, Z., Yao, J., Kosynkin, D. V. & Tour, J. M. Transforming carbon nanotube devices into nanoribbon devices. J. Am. Chem. Soc. 131, 13460–13463 (2009).
Rouquerol, F., Rouquerol, J. & Sing, K. Adsorption by Powders and Porous Solids: Principles, Methodology and Applications (Academic, 1999).
Lowell, S., Shields, J. E., Thomas, M. A. & Thommes, M. Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density (Kluwer, 2004).
Rosnes, M. H. et al. Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution. J. Mater. Chem. A 3, 4827–4839 (2015).
Zhang, W., Wu, Z.-Y., Jiang, H.-L. & Yu, S.-H. Nanowire-directed templating synthesis of metal–organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis. J. Am. Chem. Soc. 136, 14385–14388 (2014).
Chen, L. et al. One-step solid-state thermolysis of a metal–organic framework: a simple and facile route to large-scale of multiwalled carbon nanotubes. Chem. Commun. 1581–1583 (2008).
Li, J.-S. Nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrids derived from MOFs: efficient bifunctional electrocatalysts for ORR and OER. Chem. Commun. 51, 2710–2713 (2015).
Wang, G., Zhang, L. & Zhang, J. A review of electrode materials for electrochemical supercapacitors. Chem. Soc. Rev. 41, 797–828 (2012).
Gu, W. & Yushin, G. Review of nanostructured carbon materials for electrochemical capacitor applications: advantages and limitations of activated carbon, carbide-derived carbon, zeolite-templated carbon, carbon aerogels, carbon nanotubes, onion-like carbon, and graphene. WIREs Energy Environ. 3, 424–473 (2014).
Miller, J. R., Outlaw, R. A. & Holloway, B. C. Graphene double-layer capacitor with ac line-filtering performance. Science 329, 1637–1639 (2010).
The authors thank the reviewers for comments and suggestions, T. Uchida (AIST) and S.K. Soni (RMIT) for microscopic measurements, and Japan Society for the Promotion of Science (JSPS) for financial support (KAKENHI no. 26289379). D.S. and M.M. thank the Australian Research Council for partial support through an ARC Discovery grant (DP 110100082).
The authors declare no competing financial interests.
About this article
Cite this article
Pachfule, P., Shinde, D., Majumder, M. et al. Fabrication of carbon nanorods and graphene nanoribbons from a metal–organic framework. Nature Chem 8, 718–724 (2016). https://doi.org/10.1038/nchem.2515
FeCo alloy@N-doped graphitized carbon as an efficient cocatalyst for enhanced photocatalytic H2 evolution by inducing accelerated charge transfer
Journal of Energy Chemistry (2021)
Acidified bimetallic MOFs constructed Co/N co-doped low dimensional hybrid carbon networks for high-efficiency microwave absorption
Scalable fabrication and active site identification of MOF shell-derived nitrogen-doped carbon hollow frameworks for oxygen reduction
Journal of Materials Science & Technology (2021)
Highly efficient conversion of waste plastic into thin carbon nanosheets for superior capacitive energy storage
Synthesis of micro/nanoscaled metal–organic frameworks and their direct electrochemical applications
Chemical Society Reviews (2020)