Carbon Formation at High Temperatures (550–1400 °C): Kinetics, Alternative Mechanisms and Growth Modes
<p>(<b>a</b>) Three kinetic routes key points: I—Surface catalysis; II—C dissolution; III—C layers; (<b>b</b>) Typical Arrhenius plots observed experimentally with Ni, Co and Fe over a wide T range.</p> "> Figure 2
<p>Typical Arrhenius plot: carbon formation mechanisms at high temperature. Below ~850 °C (point temperature), the rate is controlled by the slower pyrolytic carbon deposition step (the carbon bulk diffusion step is faster) and carbon nanotubes (CNTs) can grow. The catalyst external surface remains clean. Above ~850 °C, the same step is faster. Pyrolytic carbon deposition on the surfaces prevails and carbon bulk diffusion is not possible: carbon layers cover the surface. However, using lower gas pressures (ex: P/10) CNTs growth can operate at higher temperatures (T<sub>h</sub> >T) and faster rates.</p> "> Figure 3
<p>Kinetic curves for the rate of decomposition of carbon against 1/T for hydrocarbons shown (adapted from reference [<a href="#B13-catalysts-10-00465" class="html-bibr">13</a>]).</p> ">
Abstract
:1. Introduction
2. Kinetic Routes, Alternative Growth Mechanisms
3. Mechanism above ~550 °C: Transition from Hybrid to Pyrolytic Growth
4. HT Deposition: Lower Active Gas Pressure, Faster CNTs Growth Rates
5. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Palmer, H.B.; Cullis, C.L. The Formation of Carbon from Gases. In Chemistry and Physics of Carbon; Dekker: New York, NY, USA, 1965; Volume 1, pp. 265–325. [Google Scholar]
- Kotlensky, W.V. Deposition of Pyrolytic Carbon in Porous Solids. In Chemistry and Physics of Carbon; Marcel Dekker, Inc.: New York, NY, USA, 1973; Volume 9, pp. 173–262. [Google Scholar]
- Bokros, J.C. Deposition, Structure and Properties of Pyrolytic Carbons. In Chemistry and Physics of Carbon; Dekker: New York, NY, USA, 1969; Volume 5. [Google Scholar]
- Barrer, R.M. Diffusion in and through Solids; Cambridge Univ. Press: Cambridge, UK, 1941. [Google Scholar]
- Walker, P.L.; Rusinko, F.; Austin, I.G. Gas Reactions of Carbon. In Advances in Catalysis; Academic Press: Cambridge, MA, USA, 1959; Volume 11, pp. 133–221. [Google Scholar]
- Slysh, R.S.; Kinney, C.R. Some kinetics of the carbonization of benzene, acetylene and diacetylene at 1200 degree. J. Phys. Chem. 1961, 65, 1044. [Google Scholar] [CrossRef]
- Ford, A.R. Deposition, Structure and Properties of Pyrolytic Carbons. Engineer 1967, 224, 444. [Google Scholar]
- Fischback, D.B. Effect of Substrate Structure on Deposition of Evaporated Carbon. J. Mater. Sci. 1968, 3, 559–561. [Google Scholar] [CrossRef] [Green Version]
- Presland, A.E.B.; Walker, P.L. Growth of single-crystal graphite by pyrolysis of acetylene over metals. Carbon 1969, 7, 1–4. [Google Scholar] [CrossRef]
- Khan, M.S.; Crynes, B.L. Survey of Recent Methane Pyrolysis Literature. Ind. Eng. Chem. 1970, 62, 54–59. [Google Scholar] [CrossRef]
- Tesner, P.A.; Robonovich, E.Y.; Rafalkes, I.S.; Arefieva, E.F. Formation of Carbon Fibers from Acetylene. Carbon 1970, 8, 435–442. [Google Scholar] [CrossRef]
- Lobo, L.S.; Trimm, D.L. Complex temperature dependencies of the rate of carbon deposition on nickel. Nat. Phys. Sci. 1971, 234, 15–16. [Google Scholar] [CrossRef]
- Lobo, L.S.; Trimm, D.L. Studies of Carbon Formation on Metals Using a Vacuum Microbalance. In Progress in Vacuum Microbalance Techniques; Heyden & Son: London, UK, 1972; Volume 2. [Google Scholar]
- Baker, R.T.; Barber, M.A.; Harris, P.S.; Feates, F.S.; Waite, R.J. Nucleation and Growth of C Deposits from Ni Catalyzed Decomposition of C2H2. J. Catal. 1972, 26, 51–62. [Google Scholar] [CrossRef]
- Nielsen, J.R.; Trimm, D.L. Mechanism of Carbon Formation on Nickel-Containing Catalysts. J. Catal. 1977, 48, 155–165. [Google Scholar]
- Iijima, S. Helical microtubules of graphitic carbon. Nature 1991, 354, 56–58. [Google Scholar] [CrossRef]
- Saito, R.; Dresselhause, G.; Dresselhause, M.S. Physical Properties of Carbon Nanotubes; Imperial College Press: London, UK, 1998. [Google Scholar]
- Harris, P.J.F. Carbon Nanotube Science; Cambridge University Press: Cambridge, UK, 2009. [Google Scholar]
- Shaikjee, A.; Coville, N.J. The role of the hydrocarbon source on the growth of carbon materials. Carbon 2012, 50, 3376–3398. [Google Scholar] [CrossRef]
- Fau, G.; Gascoin, N.; Steelant, J. Hydrocarbon pyrolysis with a methane focus: A review on the catalytic effect and the coke production. J. Anal. Appl. Pyrol. 2014, 108, 1–11. [Google Scholar] [CrossRef]
- Ashik, U.P.M.; Wan Daud, W.M.A.; Abas, H.F. Production of greenhouse gas free hydrogen by thermocatalytic decomposition of methane—A review. Renew. Sustain. Energy Rev. 2015, 44, 221–256. [Google Scholar] [CrossRef] [Green Version]
- Ashik, U.P.M.; Wan Daud, W.M.A.; Hyashi, J.-I. A review on CH4 transformation to H2 and nanocarbon. Renew. Sustain. Energy Rev. 2017, 76, 743–767. [Google Scholar] [CrossRef]
- Janas, D. Towards monochiral carbon nanotubes: A review of progress in the sorting of single-walled CNTs. Mater. Chem. Front. 2018, 2, 36–73. [Google Scholar] [CrossRef]
- Lobo, L.S. Mechanism of Catalytic CNTs Growth in 400–650 °C Range: Explaining Volcano Shape Arrhenius Plot and Catalytic Synergism Using both Pt (or Pd) and Ni, Co or Fe. C J. Carbon Res. 2019, 5, 42. [Google Scholar] [CrossRef] [Green Version]
- Lobo, L.S. Catalytic carbon formation: Clarifying the alternative kinetic routes and defining a kinetic linearity for sustained growth concept. Reac. Kinet. Mech. Cat. 2016, 118, 393–414. [Google Scholar] [CrossRef]
- Lobo, L.S. Nucleation and growth of carbon nanotubes and nanofibers: Mechanism and catalytic geometry control. Carbon 2017, 114, 411–417. [Google Scholar] [CrossRef]
- Cunha, A.F.; Orfão, J.J.M.; Figueiredo, J.L. Catalytic decomposition of methane on Raney-type catalysts. Appl. Catal. A 2008, 348, 103–112. [Google Scholar] [CrossRef]
- Figueiredo, J.L.; Orfão, J.J.M.; Cunha, A.F. H2 production via CH4 decomposition on Raney-type catalysts. Int. J. Hydrogen Energy 2010, 35, 9795–9980. [Google Scholar] [CrossRef]
- Ferreira, V.J.; Tavares, P.; Figueiredo, J.L.; Faria, J.L. Ce-Doped La2O3 based catalyst for the oxidative coupling of methane. Catal. Commun. 2013, 42, 50–53. [Google Scholar] [CrossRef]
- Lázaro, M.J.; Pinilla, J.L.; Suelves, I.; Moliner, R. Study of the deactivation mechanism of carbon blacks used in methane decomposition. Int. J. Hydrogen Energy 2008, 33, 4104–4111. [Google Scholar] [CrossRef]
- Emmenegger, C.; Bonard, J.M.; Mauron, P.; Sudan, P.; Lepora, A.; Grobety, B.; Züttel, A.; Schlapbach, L. Synthesis of carbon nanotubes over Fe catalyst on aluminium and suggested growth mechanism. Carbon 2003, 41, 539–547. [Google Scholar] [CrossRef]
- Herreyre, S.; Gadelle, P. Effect of H2 on the morphology of C deposited from the catalytic disproportionation of CO. Carbon 1995, 33, 234–237. [Google Scholar] [CrossRef]
- Rao, C.N.R.; Govindaraj, A.; Sen, R.; Satishkumar, B.C. Synthesis of MW and SW nanotubes, aligned-nanotube bundles and nanorods by employing organometallic precursors. Mat. Res. Innovat. 1998, 2, 128–141. [Google Scholar] [CrossRef] [Green Version]
- Guellati, O.; Bégin, D.; Antoni, F.; Moldovan, S.; Guerioune, M.; Pham-Huu, C. CNTs’ array growth using the floting catalyst-CVD method over different substrates and H2 supply. Mater. Sci. Eng. B 2018, 231, 11–17. [Google Scholar] [CrossRef]
- Barreiro, A.; Hampel, S.; Rümmeli, M.H.; Kramberger, C.; Grüneis, A.; Biedermann, K.; Leonhardt, A.; Gemming, T.; Büchner, B.; Bachtold, A.; et al. Thermal decomposition of Ferrocene as a Method for Production of SWCNTs without Additional Carbon Sources. J. Phys. Chem. B 2006, 110, 20973–20977. [Google Scholar] [CrossRef]
- Eres, G.; Kinkhabwala, A.A.; Cui, H.; Geohegan, D.B.; Puretzky, A.A.; Lowndes, D.H. Molecular Beam-Controlled Nucleation and Growth of Vertically Aligned SWCNTs arrays. J. Phys. Chem. B 2005, 109, 16684–16694. [Google Scholar] [CrossRef]
- Latorre, N.; Romeo, E.; Villacampa, J.I.; Cazana, F.; Royo, C.; Monzon, A. Kinetics of CNTs growth on a Ni-Mg-Al catalyst by CCVD of methane: Influence of catalyst deactivation. Catal. Today 2010, 154, 217–223. [Google Scholar] [CrossRef]
- Valiente, A.M.; Lopez, P.N.; Ramos, I.R.; Ruiz, A.G.; Li, C.; Xin, Q. In situ study of CNT formation by C2H2 decomposition on an iron-based catalyst. Carbon 2000, 38, 2003–2006. [Google Scholar] [CrossRef]
- Shi, Y.; Wang, Y.; Ren, Y.; Wan, Y. Effect of Gas Atmosphere in the Heating Stage on Limiting Nucleation of Graphene on Cu Foils by Low Pressure CVD. Cryst. Res. Technol. 2020. [Google Scholar] [CrossRef]
First Author | Year | Temperature (°C) | Catalyst | Gas | Reference |
---|---|---|---|---|---|
Shaikjee | 2012 | 600–1000 | Fe, Ni, Co | hydrocarbons | [19] |
Fau | 2014 | 500–900 | Pd, Mo, Ni, Fe | CH4 | [20] |
Ashik | 2015 | 550–900 | Fe, Co, Ni, | CH4 | [21] |
Ashik | 2017 | 550–700 | Ni, Co, Fe, Cu | CH4/H2 | [22] |
Janas | 2018 | 400–600 | Co | CO | [23] |
Kinetic Routes | Temperature Range (°C) | Order | Carbon Growth Type | Active Catalysts |
---|---|---|---|---|
I Catalytic | 300/550 low T | 0 | Surface catalysis/ graphene growth | Ni (+Cu) Fe, Co |
II Hybrid | 550/~700 intermediate | 1 | Carbon black atoms dissolve and grow | Pt, Ru, Mo, Ni |
III Pyrolytic | ~600/1200 high T | 1 | Carbon black forms successive layers | No catalysis, shape adjusts |
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Lobo, L.S.; Carabineiro, S.A.C. Carbon Formation at High Temperatures (550–1400 °C): Kinetics, Alternative Mechanisms and Growth Modes. Catalysts 2020, 10, 465. https://doi.org/10.3390/catal10050465
Lobo LS, Carabineiro SAC. Carbon Formation at High Temperatures (550–1400 °C): Kinetics, Alternative Mechanisms and Growth Modes. Catalysts. 2020; 10(5):465. https://doi.org/10.3390/catal10050465
Chicago/Turabian StyleLobo, Luís Sousa, and Sónia A. C. Carabineiro. 2020. "Carbon Formation at High Temperatures (550–1400 °C): Kinetics, Alternative Mechanisms and Growth Modes" Catalysts 10, no. 5: 465. https://doi.org/10.3390/catal10050465