Journal of Materials Science

, Volume 50, Issue 19, pp 6245–6259 | Cite as

Hierarchical porous graphitic carbon monoliths with detonation nanodiamonds: synthesis, characterisation and adsorptive properties

  • Emer Duffy
  • Xiaoyun He
  • Pavel N. Nesterenko
  • Brett PaullEmail author
Original Paper


The addition of nano-carbons to composite materials is an area of significant research interest, when their addition results in improved properties. This work reports on the use of detonation nanodiamond (DND) in the preparation of porous carbon monoliths and an investigation of the properties of the final carbon–nanocarbon composite material. Porous carbon–nanodiamond (CND) monoliths, with macro-, meso- and micropores were prepared by carbonisation of a resorcinol-formaldehyde (RF) polymeric rod with an Fe(III) catalyst and spherical silica template. Pore characteristics and BET surface areas were determined from N2 isotherms, with surface areas in the range of 214–461 m2 g−1, depending on DND content. SEM imaging further confirmed the hierarchical pore structure present, where there was a trimodal structure for monoliths containing nanodiamond following pyrolysis up to 900 °C. Thermogravimetric analysis, TEM imaging, energy dispersive X-ray electron spectroscopy and Raman spectroscopy were employed to evaluate the properties of this new composite material. The adsorptions of methylene blue (MB) and neutral red (NR) dyes from water onto the composite monoliths were investigated and compared with activated carbon in order to further evaluate their physical and adsorptive properties. CND materials adsorb these two cationic dyes more effectively than activated carbon, due to a more accessible pore network, and DND content had a direct effect on adsorption capacities for the dyes. The adsorption isotherms coincided with Langmuir and Freundlich adsorption models. Maximum adsorption capacities of 599 and 284 mg g−1 were achieved for NR and MB, respectively, on the CND composites.


Methylene Blue Total Pore Volume Porous Carbon Material Graphitic Nature Carbon Monolith 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors are grateful to the Australian Research Council for the financial support in the form of Australian Research Council Discovery Grants DP110102046 and DP150102608. E.D. would also like to thank Dr. Ekaterina P. Nesterenko and Mrs. Heather Davies for technical assistance. The authors also acknowledge the technical support imaging materials received from Dr. Satheesh Krishnamurthy (TEM), Dr. Karsten Goemann and Dr. Sandrin Feig (SEM).


  1. 1.
    Ruo-wen FU, Zheng-hui LI, Ye-ru L, Eng LI, Eei XU, Ding-cai WU (2011) Hierarchical porous carbons: design: preparation and performance in energy storage. New Carbon Mater 26:171–179CrossRefGoogle Scholar
  2. 2.
    Upare DP, Yoon S, Lee CW (2011) Nano-structured porous carbon materials for catalysis and energy storage. Korean J Chem Eng 28:731–743CrossRefGoogle Scholar
  3. 3.
    Gupta VK, Saleh TA (2013) Sorption of pollutants by porous carbon, carbon nanotubes and fullerene—an overview. Environ Sci Pollut Res 20:2828–2843CrossRefGoogle Scholar
  4. 4.
    Pereira L (2008) Porous graphitic carbon as a stationary phase in hplc: theory and applications. J Liquid Chromatogr Relat Technol 31:1687–1731CrossRefGoogle Scholar
  5. 5.
    Carneiro MC, Puignou L, Galceran MT (2000) Comparison of silica and porous graphitic carbon as solid phase extraction materials for the analysis of cationic herbicides in water by liquid chromatography and capillary electrophoresis. Anal Chim Acta 408:263–269CrossRefGoogle Scholar
  6. 6.
    Hennion MC (2000) Graphitized carbons for solid phase extraction. J Chromatogr A 885:73–95CrossRefGoogle Scholar
  7. 7.
    Eltmimi AH, Barron L, Rafferty A, Hanrahan JP, Fedyanina O, Nesterenko E, Nesterenko PN, Paull B (2010) Preparation, characterisation and modification of carbon-based monolithic rods for chromatographic applications. J Sep Sci 33:1231–1243Google Scholar
  8. 8.
    Liang C, Dai S, Guichon GA (2003) Graphitized carbon monolithic column. Anal Chem 75:4904–4912CrossRefGoogle Scholar
  9. 9.
    He X, Male KB, Nesterenko PN, Brabazon D, Paull B, Luong JHT (2013) Adsorption and desorption of methylene blue on porous carbon monoliths and nanocrystalline cellulose. ACS Appl Mater Interfaces 5:8796–8804CrossRefGoogle Scholar
  10. 10.
    Kim YS, Guo XF, Kim GJ (2010) Synthesis of carbon monolith with bimodal meso/macroscopic pore structure and its application in asymmetric catalysis. Catal Today 150:91–99CrossRefGoogle Scholar
  11. 11.
    Garcia-Gomez A, Miles P, Centeno TA, Rojo JM (2010) Why carbon monoliths are better supercapacitor electrodes than compacted pellets. Electrochem Solid State Lett 13:112–114CrossRefGoogle Scholar
  12. 12.
    Guichon G (2007) Monolithic columns in high-performance liquid chromatography. J Chromatogr A 1168:101–168CrossRefGoogle Scholar
  13. 13.
    Kilduff JE, Karanfil T, Chin Y-P, Weber WJ (1996) Adsorption of natural organic polyelectrolytes by activated carbon: a size-exclusion chromatography study. Environ Sci Technol 30:1336–1343CrossRefGoogle Scholar
  14. 14.
    Taguchi A, Smått JH, Lindén M (2003) Carbon monoliths possessing a hierarchical fully interconnected porosity. Adv Mater 15:1209–1211CrossRefGoogle Scholar
  15. 15.
    Nesterenko EP, Nesterenko PN, Connolly D, He X, Floris P, Duffy E, Paull B (2013) Nano-particle modified stationary phases for high-performance liquid chromatography. Analyst 138:4229–4254CrossRefGoogle Scholar
  16. 16.
    Herrera-Herrera AV, Gonzalez-Curbelo MA, Hernández-Borges J, Rodríguez-Delgado MA (2012) Carbon nanotubes applications in separation science: a review. Anal Chim Acta 734:1–30CrossRefGoogle Scholar
  17. 17.
    Scida K, Stege PW, Haby G, Messina GA, Garcia CD (2011) Recent applications of carbon-based nanomaterials in analytical chemistry: critical review. Anal Chim Acta 691:6–17CrossRefGoogle Scholar
  18. 18.
    Valcarel M, Cardenas S, Simonet BM, Moliner-Martinez Y, Lucena R (2008) Carbon nanostructures as sorbent materials in analytical processes. TrAC 27:34–43Google Scholar
  19. 19.
    Namera A, Nakamoto A, Saito T, Miyazaki S (2011) Monolith as a new sample preparation material: recent devices and applications. J Sep Sci 34:901–924CrossRefGoogle Scholar
  20. 20.
    Moreno-Castilla C, Perez-Cadenas AF (2010) Carbon-based honeycomb monoliths for environmental gas-phase applications. Materials 3:1203–1227CrossRefGoogle Scholar
  21. 21.
    Knox JH, Gilbert MT (1979) US Patent 4263268Google Scholar
  22. 22.
    Saleh TA, Gupta VK (2014) Processing methods, characteristics and adsorption behaviour of tire derived carbons: a review. Adv Colloid Interface Sci 211:93–101CrossRefGoogle Scholar
  23. 23.
    Yagub MT, Sen TK, Afroze S, Ang HM (2014) Dye and its removal from aqueous solution by adsorption: a review. Adv Colloid Interface Sci 209:172–184CrossRefGoogle Scholar
  24. 24.
    Liu F, Xu Z, Wan H, Wan Y, Zheng S, Zhu D (2011) Enhanced adsorption of humic acids on ordered mesoporous carbon compared with microporous activated carbon. Environ Toxicol Chem 30:793–800CrossRefGoogle Scholar
  25. 25.
    Han S, Sohn K, Hyeon T (2000) Fabrication of new nanoporous carbons through silica templates and their application to the adsorption of bulky dyes. Chem Mater 12:3337–3341CrossRefGoogle Scholar
  26. 26.
    Sevilla M, Fuertes AB (2013) Fabrication of porous carbon monoliths with a graphitic framework. Carbon 56:155–166CrossRefGoogle Scholar
  27. 27.
    Sakintuna B, Yürüm Y (2005) Templated porous carbons: a review article. Ind Eng Chem Res 44:2893–2902CrossRefGoogle Scholar
  28. 28.
    Alvarez S, Fuertes AB (2007) Synthesis of macro/mesoporous silica and carbon monoliths by using a commercial polyurethane foam as sacrificial template. Mater Lett 61:2378–2381CrossRefGoogle Scholar
  29. 29.
    Tao S, Wang Y, Shi D, An Y, Qiu J, Zhao Y, Cao Y, Zhang X (2014) Facile synthesis of highly graphitized porous carbon monoliths with a balance on crystallization and pore-structure. J Mater Chem A 2:12785–12791CrossRefGoogle Scholar
  30. 30.
    He X, Nesterenko EP, Nesterenko PN, Brabazon D, Zhou L, Glennon JD, Luong JHT, Paull B (2013) Fabrication and characterization of nanotemplated carbon monolithic material. ACS Appl Mater Interfaces 5:8572–8580CrossRefGoogle Scholar
  31. 31.
    Duffy E, He X, Nesterenko EP, Dey A, Krishnamurthy S, Brabazon D, Nesterenko PN, Paull B (2015) Thermally controlled growth of carbon onions within porous graphitic carbon-detonation nanodiamond monolithic composites. RSC Adv 5:22906–22915CrossRefGoogle Scholar
  32. 32.
    Nesterenko PN, Haddad PR (2010) Diamond-related materials as potential new media in separation science. Anal Bioanal Chem 396:205–211CrossRefGoogle Scholar
  33. 33.
    Mochalin VM, Shenderova O, Ho D, Gogotsi Y (2012) The properties and applications of nanodiamonds. Nat Nanotechnol 7:11–23CrossRefGoogle Scholar
  34. 34.
    Krueger A (2008) Diamond nanoparticles: jewels for chemistry and physics. Adv Mater 20:2445–2449CrossRefGoogle Scholar
  35. 35.
    Peristyy AA, Fedyanina O, Paull B, Nesterenko PN (2014) Diamond based adsorbents and their application in chromatography. J Chromatogr A 1357:68–86CrossRefGoogle Scholar
  36. 36.
    Wang DH, Tan L-S, Huang H, Dai L, Osawa E (2009) In-situ nanocomposite synthesis: arylcarbonylation and grafting of primary diamond nanoparticles with a poly(ether-ketone) in polyphosphoric acid. Macromolecules 42:114–124CrossRefGoogle Scholar
  37. 37.
    Shenderova O, Jones C, Borjanovic V, Hens S, Cunningham G, Moseenkov S, Kuznetsov V, McGuire G (2008) Detonation nanodiamond and onion-line carbon: applications in composites. Physica Status Solidi (a) 205:2245–2251CrossRefGoogle Scholar
  38. 38.
    Manandhar S, Roder PB, Hanson JL, Lim M, Smith BE, Mann A, Pauzauskie PJ (2014) Rapid sol-gel synthesis of nanodiamond aerogel. J Mater Res 29:2905–2911CrossRefGoogle Scholar
  39. 39.
    Ostrovidova GU, Makeev AV, Biryukov AV, Gordeev SK (2003) Carbon nanocomposite materials as medicinal depot. Mater Sci Eng C 23:377–381CrossRefGoogle Scholar
  40. 40.
    Shenderova OA, Zhirnov VV, Brenner DW (2002) Carbon nanostructures. Crit Rev Solid State Mater Sci 27:227–356CrossRefGoogle Scholar
  41. 41.
    Choma J, Jedynak K, Fahrenholz W, Ludwinowicz J, Jaroniec M (2014) Microporosity development in phenolic resin-based mesoporous carbons for enhancing CO2 adsorption at ambient conditions. Appl Surf Sci 289:592–600CrossRefGoogle Scholar
  42. 42.
    Sajad M, Kazemzad M, Hosseinnia A (2014) Preparation of activated carbon monolith by application of phenolic resins as carbon precursors. Funct Mater Lett 7:1450035CrossRefGoogle Scholar
  43. 43.
    Robertson C, Mokaya R (2013) Microporous activated carbon aerogels via a simple subcritical drying route for CO2 capture and hydrogen storage. Microporous Mesoporous Mater 179:151–156CrossRefGoogle Scholar
  44. 44.
    Kipling JJ, Wilson RB (1960) Adsorption of methylene blue in the determination of surface areas. J Appl Chem 10:109–113CrossRefGoogle Scholar
  45. 45.
    Los JM, Tompkins CK (1956) Adsorption of methylene blue on a positively charged mercury surface. J Chem Phys 24:630CrossRefGoogle Scholar
  46. 46.
    Taha-Tijerina JJ, Narayanan TN, Tiwary CS, Lozano K, Chipara M, Ajayan PM (2014) Nanodiamond-based thermal fluids. ACS Appl Mater Interfaces 6:4778–4785CrossRefGoogle Scholar
  47. 47.
    Branson BT, Beauchamp PS, Beam JC, Lukehart CM, Davidson JL (2013) Nanodiamond nanofluids for enhanced thermal conductivity. ACS Nano 7:3183–3189CrossRefGoogle Scholar
  48. 48.
    Barnard AS (2008) Self-assembly in nanodiamond agglutinates. J Mater Chem 18:4038–4041CrossRefGoogle Scholar
  49. 49.
    Duffy E, Mitev D, Kazarian AA, Nesterenko PN, Paull B (2014) Separation and characterisation of detonation nanodiamond by capillary zone electrophoresis. Electrophoresis 35:1864–1872CrossRefGoogle Scholar
  50. 50.
    Kuznetsov VL, Chuvilin AL, Butenko YV, Mal’kov IY, Titov VM (1994) Onion-like carbon from ultra-disperse diamond. Chem Phys Lett 222:343–348CrossRefGoogle Scholar
  51. 51.
    Chen J, Deng SZ, Chen J, Yu ZX, Xu NS (1994) Graphitization of nanodiamond powder annealed in argon ambient. Appl Phys Lett 74:3651–3653CrossRefGoogle Scholar
  52. 52.
    Lowell S, Shields JE, Thomas MA, Thommes M (2004) Characterization of porous solids and powders: surface area, pore size and density. Kluwer Academic Publishers, LondonCrossRefGoogle Scholar
  53. 53.
    Ko T-H, Kuo W-S, Chang Y-H (2001) Microstructural changes of phenolic resin during pyrolysis. J Appl Polym Sci 81:1084–1089CrossRefGoogle Scholar
  54. 54.
    Batsanov SS, Lesnikov EV, Dan’kin DA, Balakhanov DM (2014) Water shells of diamond nanoparticles in colloidal solutions. Appl Phys Lett 104:133105CrossRefGoogle Scholar
  55. 55.
    Fang XW, Mao JD, Levin EM, Schmidt-Rohr K (2009) Nonaromatic core-shell structure of nanodiamond from solid-state NMR spectroscopy. J Am Chem Soc 131:1426–1435CrossRefGoogle Scholar
  56. 56.
    Ko TH, Kuo WS, Lu YR (2000) The influence of post-cure on properties of carbon/phenolic resin cured composites and their final carbon/carbon composites. Polym Compos 21:96–103CrossRefGoogle Scholar
  57. 57.
    Mitev DM, Townsend AT, Paull B, Nesterenko PN (2014) Microwave-assisted purification of detonation nanodiamond. Diam Relat Mater 48:37–46CrossRefGoogle Scholar
  58. 58.
    Xu NS, Chen J, Deng SZ (2002) Effect of heat treatment on the properties of nano-diamond under oxygen and argon ambient. Diam Relat Mater 11:249–256CrossRefGoogle Scholar
  59. 59.
    Tuinstra F, Koenig JL (1970) Raman spectrum of graphite. J Chem Phys 53:1126–1130CrossRefGoogle Scholar
  60. 60.
    Ferrari AC, Robertson J (2000) Interpretation of raman spectra of disordered and amorphous carbon. Phys Rev B 61:14095–14107CrossRefGoogle Scholar
  61. 61.
    Yuan X, Shu-Ping Z, Wei X, Hong-You C, Xiao-Dong D, Xin-Mei L, Zi-Feng Y (2007) Aqueous dye adsorption on ordered mesoporous carbons. J Colloid Interface Sci 310:83–89CrossRefGoogle Scholar
  62. 62.
    Wu F-C, Tseng R-L, Juang R-S (2005) Preparation of highly microporous carbons from fir wood by KOH activation for adsorption of dyes and phenols from water. Sep Purif Technol 47:10–19CrossRefGoogle Scholar
  63. 63.
    Dabrowski A (2001) Adsorption—from theory to practice. Adv Colloid Interface Sci 93:135–224CrossRefGoogle Scholar
  64. 64.
    Wang S, Wei J, Lv S, Guo Z, Jiang F (2013) Removal of organic dyes in environmental water onto magnetic-sulfonic graphene nanocomposite. CLEAN 41:751–764Google Scholar
  65. 65.
    Desta MB (2013) Batch sorption experiments: langmuir and freundlich isotherm studies for the adsorption of textile metal ions onto teff straw (Eragrostis Tef) agricultural waste. J Thermodyn 2013:375830Google Scholar
  66. 66.
    Poots VJP, McKay G, Healy JJ (1978) Removal of basic dye from effluent using wood as an adsorbent. J Water Pollut Control F 50:926–935Google Scholar
  67. 67.
    Hall KR, Eagleton LC, Acrivos A, Vermeulen T (1966) Pore- and solid-diffusion kinetics in fixed-bed adsorption under constant-pattern conditions. Ind Eng Chem Fundamen 5:212–223CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  1. 1.Australian Centre for Research on Separation ScienceUniversity of TasmaniaHobartAustralia
  2. 2.Irish Separation Science Cluster, National Centre for Sensor ResearchDublin City UniversityDublin 9Ireland
  3. 3.ARC Centre of Excellence for Electromaterials ScienceUniversity of TasmaniaHobartAustralia

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