Review Article | Published:

Molecular-based design and emerging applications of nanoporous carbon spheres

Nature Materials volume 14, pages 763774 (2015) | Download Citation

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Abstract

Over the past decade, considerable progress has been made in the synthesis and applications of nanoporous carbon spheres ranging in size from nanometres to micrometres. This Review presents the primary techniques for preparing nanoporous carbon spheres and the seminal research that has inspired their development, presented potential applications and uncovered future challenges. First we provide an overview of the synthesis techniques, including the Stöber method and those based on templating, self-assembly, emulsion and hydrothermal carbonization, with special emphasis on the design and functionalization of nanoporous carbon spheres at the molecular level. Next, we cover the key applications of these spheres, including adsorption, catalysis, separation, energy storage and biomedicine — all of which might benefit from the regular geometry, good liquidity, tunable porosity and controllable particle-size distribution offered by nanoporous carbon spheres. Finally, we present the current challenges and opportunities in the development and commercial applications of nanoporous carbon spheres.

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References

  1. 1.

    & Chemically tailorable colloidal particles from infinite coordination polymers. Nature 438, 651–654 (2005).

  2. 2.

    , & Recent progress in the synthesis of porous carbon materials. Adv. Mater. 18, 2073–2094 (2006).

  3. 3.

    , & Carbon spheres. Mater. Sci. Eng. R 70, 1–28 (2010).

  4. 4.

    , , & Carbon nanospheres: Synthesis, physicochemical properties and applications. J. Mater. Chem. 21, 1664–1672 (2011).

  5. 5.

    , , , & Chemical synthesis of carbon materials with intriguing nanostructure and morphology. Macromol. Chem. Phys. 213, 1107–1131 (2012).

  6. 6.

    et al. Structurally ordered mesoporous carbon nanoparticles as transmembrane delivery vehicle in human cancer cells. Nano Lett. 8, 3724–3727 (2008).

  7. 7.

    et al. A low-concentration hydrothermal synthesis of biocompatible ordered mesoporous carbon nanospheres with tunable and uniform size. Angew. Chem. Int. Ed. 49, 7987–7991 (2010).

  8. 8.

    et al. A facile soft-template synthesis of mesoporous polymeric and carbonaceous nanospheres. Nature Commun. 4, 3798 (2013).

  9. 9.

    & Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles. Angew. Chem. Int. Ed. 43, 597–601 (2004).

  10. 10.

    , , & Highly monodisperse microporous polymeric and carbonaceous nanospheres with multifunctional properties. Sci. Rep. 3, 1430 (2013).

  11. 11.

    et al. Temperature-programmed precise control over the sizes of carbon nanospheres based on benzoxazine chemistry. J. Am. Chem. Soc. 133, 15304–15307 (2011).

  12. 12.

    et al. Extension of the Stöber method to the preparation of monodisperse resorcinol-formaldehyde resin polymer and carbon spheres. Angew. Chem. Int. Ed. 50, 5947–5951 (2011).

  13. 13.

    et al. New opportunities in Stöber synthesis: preparation of microporous and mesoporous carbon spheres. J. Mater. Chem. 22, 12636–12642 (2012).

  14. 14.

    et al. Controlled synthesis of mesoporous carbon nanostructures via a 'silica-assisted' strategy. Nano Lett. 13, 207–212 (2013).

  15. 15.

    , & One-step synthesis of silica@resorcinol-formaldehyde spheres and their application for the fabrication of polymer and carbon capsules. Chem. Commun. 48, 6124–6126 (2012).

  16. 16.

    et al. Gold nanoparticle–colloidal carbon nanosphere hybrid material: Preparation, characterization, and application for an amplified electrochemical immunoassay. Adv. Funct. Mater. 18, 2197–2204 (2008).

  17. 17.

    , , & Ordered mesoporous carbons. Adv. Mater. 13, 677–681 (2001).

  18. 18.

    , & Mesoporous carbon materials: Synthesis and modification. Angew. Chem. Int. Ed. 47, 3696–3717 (2008).

  19. 19.

    , & Supramolecular aggregates as templates: Ordered mesoporous polymers and carbons. Chem. Mater. 20, 932–945 (2008).

  20. 20.

    , & Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation. J. Phys. Chem. B 103, 7743–7746 (1999).

  21. 21.

    , & Direct synthesis of shaped carbon nanoparticles with ordered cubic mesostructure. Nano Lett. 7, 3223–3226 (2007).

  22. 22.

    , , , & Hydrophilic mesoporous carbon nanoparticles as carriers for sustained release of hydrophobic anti-cancer drugs. Chem. Commun. 47, 2101–2103 (2011).

  23. 23.

    et al. Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium–sulfur batteries. Angew. Chem. Int. Ed. 51, 3591–3595 (2012).

  24. 24.

    et al. General synthesis of discrete mesoporous carbon microspheres through a confined self-assembly process in inverse opals. ACS Nano 7, 8706–8714 (2013).

  25. 25.

    , , & Functional hollow carbon nanospheres by latex templating. J. Am. Chem. Soc. 132, 17360–17363 (2010).

  26. 26.

    et al. Dopamine as a carbon source: The controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites. Angew. Chem. Int. Ed. 50, 6799–6802 (2011).

  27. 27.

    et al. Thin-walled, mesoporous and nitrogen-doped hollow carbon spheres using ionic liquids as precursors. J. Mater. Chem. A 1, 1045–1047 (2013).

  28. 28.

    et al. Precisely controlled resorcinol-formaldehyde resin coating for fabricating core-shell, hollow, and yolk-shell carbon nanostructures. Nanoscale 5, 6908–6916 (2013).

  29. 29.

    , , & Composite of sulfur impregnated in porous hollow carbon spheres as the cathode of Li-S batteries with high performance. Nano Res. 6, 38–46 (2013).

  30. 30.

    et al. Sol–gel coating of inorganic nanostructures with resorcinol-formaldehyde resin. Chem. Commun. 49, 5135–5137 (2013).

  31. 31.

    et al. Synthesis of nitrogen-doped hollow carbon nanospheres for CO2 capture. Chem. Commun. 50, 329–331 (2014).

  32. 32.

    , & Synthesis of uniform mesoporous carbon capsules by carbonization of organosilica nanospheres. Chem. Mater. 22, 2526–2533 (2010).

  33. 33.

    , , , & Synthesis of a large-scale highly ordered porous carbon film by self-assembly of block copolymers. Angew. Chem. Int. Ed. 43, 5785–5789 (2004).

  34. 34.

    , , & Synthesis of ordered mesoporous carbons with channel structure from an organic-organic nanocomposite. Chem. Commun. 2125–2127 (2005).

  35. 35.

    et al. Ordered mesoporous polymers and homologous carbon frameworks: Amphiphilic surfactant templating and direct transformation. Angew. Chem. Int. Ed. 44, 7053–7059 (2005).

  36. 36.

    et al. An aqueous emulsion route to synthesize mesoporous carbon vesicles and their nanocomposites. Adv. Mater. 22, 833–837 (2010).

  37. 37.

    , , , & One-step synthesis of ordered mesoporous carbonaceous spheres by an aerosol-assisted self-assembly. Chem. Commun. 2867–2869 (2007).

  38. 38.

    et al. A general 'surface-locking' approach toward fast assembly and processing of large-sized, ordered, mesoporous carbon microspheres. Angew. Chem. Int. Ed. 52, 13764–13768 (2013).

  39. 39.

    et al. Hollow carbon nanoparticles of tunable size and wall thickness by hydrothermal treatment of α-cyclodextrin templated by F127 block copolymers. Chem. Mater. 25, 704–710 (2013).

  40. 40.

    et al. Engineering carbon materials from the hydrothermal carbonization process of biomass. Adv. Mater. 22, 813–828 (2010).

  41. 41.

    , , , & Hydrothermal syntheses of colloidal carbon spheres from cyclodextrins. J. Phys. Chem. C 112, 14236–14240 (2008).

  42. 42.

    et al. Cobalt–carbon spheres: Pyrolysis of dicobalthexacarbonyl-functionalized poly(p-phenyleneethynylene)s. Adv. Mater. 17, 1052–1055 (2005).

  43. 43.

    , & Recent developments in fabrication and applications of colloid based composite particles. J. Mater. Chem. 21, 615–627 (2011).

  44. 44.

    , & Can carbon spheres be created through the Stöber method? Angew. Chem. Int. Ed. 50, 9023–9025 (2011).

  45. 45.

    et al. A template-free and surfactant-free method for high-yield synthesis of highly monodisperse 3-aminophenol-formaldehyde resin and carbon nano/microspheres. Macromolecules 46, 140–145 (2013).

  46. 46.

    et al. A seeded synthetic strategy for uniform polymer and carbon nanospheres with tunable sizes for high performance electrochemical energy storage. Chem. Commun. 49, 3043–3045 (2013).

  47. 47.

    et al. Facile preparation and ultra-microporous structure of melamine-resorcinol-formaldehyde polymeric microspheres. Chem. Commun. 49, 3763–3765 (2013).

  48. 48.

    & Preparation of monodisperse, submicrometer carbon spheres by pyrolysis of melamine-formaldehyde resin. Small 2, 859–863 (2006).

  49. 49.

    , , , & Sp2 C-dominant N-doped carbon sub-micrometer spheres with a tunable size: A versatile platform for highly efficient oxygen-reduction catalysts. Adv. Mater. 25, 998–1003 (2013).

  50. 50.

    et al. Polydopamine spheres as active templates for convenient synthesis of various nanostructures. Small 9, 596–603 (2013).

  51. 51.

    , , , & Facile fabrication of core–shell-structured Ag@carbon and mesoporous yolk–shell-structured Ag@carbon@silica by an extended Stöber method. Chem. Eur. J. 19, 6942–6945 (2013).

  52. 52.

    , , , & A versatile cooperative template-directed coating method to construct uniform microporous carbon shells for multifunctional core–shell nanocomposites. Nanoscale 5, 2469–2475 (2013).

  53. 53.

    , , & Easy synthesis of hollow core, bimodal mesoporous shell carbon nanospheres and their application in supercapacitor. Chem. Commun. 47, 12364–12366 (2011).

  54. 54.

    et al. Ultrafast hydrothermal synthesis of high quality magnetic core phenol-formaldehyde shell composite microspheres using the microwave method. Langmuir 28, 10565–10572 (2012).

  55. 55.

    et al. Weak acid–base interaction induced assembly for the synthesis of diverse hollow nanospheres. Chem. Mater. 23, 4537–4542 (2011).

  56. 56.

    et al. Synthesis of nitrogen-doped mesoporous carbon spheres with extra-large pores through assembly of diblock copolymer micelles. Angew. Chem. Int. Ed. 54, 588–593 (2015).

  57. 57.

    & Design of polymeric nanoparticles for biomedical delivery applications. Chem. Soc. Rev. 41, 2545–2561 (2012).

  58. 58.

    et al. Sulfonated hollow sphere carbon as an efficient catalyst for acetalisation of glycerol. J. Mater. Chem. A 1, 9422–9426 (2013).

  59. 59.

    , , , & Carbon–gold core–shell structures: Formation of shells consisting of gold nanoparticles. Chem. Commun. 48, 3972–3974 (2012).

  60. 60.

    et al. Uniform hierarchical MoO2/carbon spheres with high cycling performance for lithium ion batteries. J. Mater. Chem. A 1, 12038–12043 (2013).

  61. 61.

    et al. Synthesis of multifunctional Ag@Au@phenol formaldehyde resin particles loaded with folic acids for photothermal therapy. Chem. Eur. J. 18, 9294–9299 (2012).

  62. 62.

    et al. Nanocomposite of MoS2 on ordered mesoporous carbon nanospheres: A highly active catalyst for electrochemical hydrogen evolution. Electrochem. Commun. 22, 128–132 (2012).

  63. 63.

    , & Preparation of Ni-doped carbon nanospheres with different surface chemistry and controlled pore structure. Appl. Surf. Sci. 254, 3993–4000 (2008).

  64. 64.

    & Facile synthesis of polymer and carbon spheres decorated with highly dispersed metal nanoparticles. Chem. Commun. 50, 12341–12343 (2014).

  65. 65.

    , , , & Synthesis and characterization of core–shell selenium/carbon colloids and hollow carbon capsules. Chem. Eur. J. 12, 548–552 (2006).

  66. 66.

    et al. Nitrogen-containing microporous carbon nanospheres with improved capacitive properties. Energy Environ. Sci. 4, 717–724 (2011).

  67. 67.

    et al. Nitrogen enriched porous carbon spheres: Attractive materials for supercapacitor electrodes and CO2 adsorption. Chem. Mater. 26, 2820–2828 (2014).

  68. 68.

    , , & Nitrogen modification of highly porous carbon for improved supercapacitor performance. J. Mater. Chem. 22, 9884–9889 (2012).

  69. 69.

    & Tailoring microporosity and nitrogen content in carbons for achieving high uptake of CO2 at ambient conditions. Adsorption 20, 287–293 (2013).

  70. 70.

    , , & A one-pot hydrothermal synthesis of tunable dual heteroatom-doped carbon microspheres. Green Chem. 14, 741–749 (2012).

  71. 71.

    , , , & Cysteine-assisted tailoring of adsorption properties and particle size of polymer and carbon spheres. Langmuir 29, 4032–4038 (2013).

  72. 72.

    et al. Easy synthesis of hollow polymer, carbon, and graphitized microspheres. Angew. Chem. Int. Ed. 49, 1615–1618 (2010).

  73. 73.

    et al. Cobalt monoxide-doped porous graphitic carbon microspheres for supercapacitor application. Sci. Rep. 3, 2925 (2013).

  74. 74.

    , , & Chemical vapor deposition of mesoporous graphene nanoballs for supercapacitor. ACS Nano 7, 6047–6055 (2013).

  75. 75.

    , , , & Nanostructured materials for advanced energy conversion and storage devices. Nature Mater. 4, 366–377 (2005).

  76. 76.

    Thermal properties of graphene and nanostructured carbon materials. Nature Mater. 10, 569–581 (2011).

  77. 77.

    et al. Carbon materials for chemical capacitive energy storage. Adv. Mater. 23, 4828–4850 (2011).

  78. 78.

    & Carbon-based materials as supercapacitor electrodes. Chem. Soc. Rev. 38, 2520–2531 (2009).

  79. 79.

    et al. Hollow carbon nanospheres with superior rate capability for sodium-based batteries. Adv. Energy Mater. 2, 873–877 (2012).

  80. 80.

    et al. Tailoring porosity in carbon nanospheres for lithium-sulfur battery cathodes. ACS Nano 7, 10920–10930 (2013).

  81. 81.

    et al. Nanostructured high-energy cathode materials for advanced lithium batteries. Nature Mater. 11, 942–947 (2012).

  82. 82.

    et al. Hydrothermal carbons from hemicellulose-derived aqueous hydrolysis products as electrode materials for supercapacitors. ChemSusChem 6, 374–382 (2013).

  83. 83.

    , , , & An experimental investigation of the ion storage/transfer behavior in an electrical double-layer capacitor by using monodisperse carbon spheres with microporous structure. J. Phys. Chem. C 116, 26791–26799 (2012).

  84. 84.

    , , , & Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries. Angew. Chem. Int. Ed. 50, 5904–5908 (2011).

  85. 85.

    et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nature Nanotech. 9, 618–623 (2014).

  86. 86.

    et al. Polydopamine-coated, nitrogen-doped, hollow carbon sulfur double-layered core–shell structure for improving lithium sulfur batteries. Nano Lett. 14, 5250–5256 (2014).

  87. 87.

    et al. Highly ordered meso@microporous carbon-supported sulfur@smaller sulfur core–shell structured cathode for Li-S batteries. ACS Nano 8, 9295–9303 (2014).

  88. 88.

    et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature Nanotech. 9, 187–192 (2014).

  89. 89.

    et al. Hydrothermal carbon spheres containing silicon nanoparticles: Synthesis and lithium storage performance. Chem. Commun. 3759–3761 (2008).

  90. 90.

    et al. Tin-nanoparticles encapsulated in elastic hollow carbon spheres for high-performance anode material in lithium-ion batteries. Adv. Mater. 20, 1160–1165 (2008).

  91. 91.

    , , , & A yolk–shell Fe3O4@C composite as an anode material for high-rate lithium batteries. ChemPlusChem 77, 748–751 (2012).

  92. 92.

    et al. Pt nanoparticles supported on nitrogen-doped porous carbon nanospheres as an electrocatalyst for fuel cells. Chem. Mater. 22, 832–839 (2010).

  93. 93.

    & Preparation of Mo-embedded mesoporous carbon microspheres for Friedel–Crafts alkylation. J. Phys. Chem. C 116, 7767–7775 (2012).

  94. 94.

    et al. Fischer–Tropsch synthesis: Iron catalysts supported on N-doped carbon spheres prepared by chemical vapor deposition and hydrothermal approaches. J. Catal. 311, 80–87 (2014).

  95. 95.

    , , , & Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation. Nature Commun. 4, 2390 (2013).

  96. 96.

    & Importance of small micropores in CO2 capture by phenolic resin-based activated carbon spheres. J. Mater. Chem. A 1, 112–116 (2013).

  97. 97.

    & Activated carbon spheres for CO2 adsorption. ACS Appl. Mater. Interfaces 5, 1849–1855 (2013).

  98. 98.

    et al. Dual-pore mesoporous carbon@silica composite core–shell nanospheres for multidrug delivery. Angew. Chem. Int. Ed. 53, 5366–5370 (2014).

  99. 99.

    et al. Colloidal RBC-shaped, hydrophilic, and hollow mesoporous carbon nanocapsules for highly efficient biomedical engineering. Adv. Mater. 26, 4294–4301 (2014).

  100. 100.

    , , & Therapeutic applications of low-toxicity spherical nanocarbon materials. NPG Asia Mater. 6, e84 (2014).

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Acknowledgements

This work was financially supported by the Australian Research Council (ARC) Discovery Project program (DP130104459). J.L. gratefully acknowledges Curtin University Pro Vice-Chancellor Awards for Research Excellence.

Author information

Affiliations

  1. Department of Chemical Engineering, Curtin University, Perth, Western Australia 6845, Australia

    • Jian Liu
  2. Department of Chemistry and Biochemistry, Kent State University, Kent, Ohio 44242, USA

    • Nilantha P. Wickramaratne
    •  & Mietek Jaroniec
  3. School of Chemical Engineering, University of Adelaide, Adelaide, South Australia 5005, Australia

    • Shi Zhang Qiao

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Contributions

J.L. and M.J. designed the initial outline of the Review. All authors discussed the contents, conceived figures and tables, wrote specific sections and proofread the article. M.J. coordinated the writing and integrated each author's contributions.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Mietek Jaroniec.

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https://doi.org/10.1038/nmat4317

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