Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter October 14, 2017

Effect of the Operating Conditions on the Growth of Carbonaceous Nanomaterials over Stainless Steel Foams. Kinetic and Characterization Studies

  • Nieves Latorre , Fernando Cazaña , Víctor Sebastián , Carlos Royo , Eva Romeo and Antonio Monzón EMAIL logo

Abstract

This work is an advance on the development of structured catalytic reactors. Here, we present the results of the effect of the main operational variables (reaction temperature, % H2 and % C2H6) on the kinetics of carbonaceous nanomaterials (CNMs) formation by catalytic decomposition of ethane over stainless steel foams. Some of the main drawback problems that occur during the operation of chemical structured reactors are related to the preparation of long term stable coatings. The washcoating is the most used technique to deposit the catalytic layer over the substrate. The application of this procedure is quite complex in the case of geometries such as foams or cloths. In the case of the deposition of layers of carbonaceous nanomaterials, an alternative route, avoiding the washcoating, is their direct growth by catalytic decomposition of light hydrocarbons over the surface of the metallic substrate. In the case of structured steel foams, the substrate already contains the catalytic active phases for this reaction, like Fe and Ni, among of the minor components (Cr, Mn, Mo) that can act as promotors/stabilizers.

The nanomaterials obtained after reaction were characterized by Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The characterization results indicate that there is a maximum, obtained at ca. 900 °C, 33.3 % of C2H6 and 1.7 % of H2, in the quality of the carbonaceous nanomaterials grown. Under these conditions, the CNMs consist mainly of few layer graphene (FLG) and graphite nanolayers (GNL) encapsulating the metallic nanoparticles. In addition, the kinetic results indicate the existence of another optimum, at ca. 800 °C, 33.3 % of C2H6 and 1.7 % of H2, in the productivity to the carbonaceous nanomaterials. The existence of these optimums is due to the driving force for the diffusion of the carbon atoms through the Fe-Ni nanoparticles (NPs) obtained at high temperatures (e. g. above 800 °C) caused by the competence between two opposite phenomena: the increase of the rate of carbon diffusion through the metallic nanoparticles of Fe-Ni and the deactivation of these nanoparticles. The deactivation is the consequence of the encapsulation and reconstruction of the nanoparticles during the formation of the several types of CNMs. The evolution of the carbon mass during the reaction time was analyzed using a phenomenological kinetic model that takes into account the main stages involved during the formation of carbonaceous nanomaterials: hydrocarbon decomposition, carburization, diffusion, precipitation and deactivation. The results obtained from the kinetic model, along with the characterization results, enable quantify the influence of the operating variables on each stage of the carbonaceous nanomaterial formation and therefore open the way to optimize the process.

Acknowledgements

The authors acknowledge financial support from MINECO (Madrid, Spain) FEDER, Project ENE2013-47880-C3-1-R.

References

Alstrup, I.J. 1988. “A New Model Explaining Carbon Filament Growth on Nickel, Iron, and Ni-Cu Alloy Catalysts.” Journal of Catalysis 109:241–251.10.1016/0021-9517(88)90207-2Search in Google Scholar

Amadou, J., D. Begin, P. Nguyen, J.P. Tessonnier, T. Dintzer, E. Vanhaecke, M.J. Ledoux, and C. Pham-Huu. 2006. “Synthesis of a Carbon Nanotube Monolith with Controlled Macroscopic Shape.” Carbon 44 (12):2587–2592.10.1016/j.carbon.2006.05.042Search in Google Scholar

Armenise, S., E. García-Bordejé, J.L. Valverde, E. Romeo, and A. Monzón. 2013. “A Langmuir–Hinshelwood Approach to the Kinetic Modelling of Catalytic Ammonia Decomposition in an Integral Reactor.” PhysChem Chemical Physical 15:12104–12117.10.1039/c3cp50715gSearch in Google Scholar

Baddour, C.E., and C. Briens. 2005a. “Carbon Nanotube Synthesis: A Review Int.” International Journal of Chemical Reactor Engineering 3 (1):R3.10.2202/1542-6580.1279Search in Google Scholar

Baddour, C.E., F. Fadlallah, D. Nasuhoglu, R. Mitra, L. Vandsburger, and J.L. Meunier. 2009. Carbon 47 (1):313–318.10.1016/j.carbon.2008.10.038Search in Google Scholar

Baddour, C.E., D.C. Upham, and J.L. Meunier. 2010. “Direct and Repetitive Growth Cycles of Carbon Nanotubes on Stainless Steel Particles by Chemical Vapor Deposition in a Fluidized Bed.” Carbon 48 (9):2652–2656.10.1016/j.carbon.2010.03.031Search in Google Scholar

Boix, A.V., J.M. Zamaro, E.A. Lombardo, and E.E. Miró. 2003. “The Beneficial Effect of Silica on the Activity and Thermal Stability of PtCoFerrierite-washcoated Cordierite Monoliths for the SCR of NOx with CH4.” Applied Catalysis B 46:121–132.10.1016/S0926-3373(03)00216-9Search in Google Scholar

Cazaña, F., N. Latorre, P. Tarifa, J. Labarta, E. Romeo, and A. Monzón. 2017. “Synthesis of Pd-Al/biomorphic Carbon Catalysts Using Cellulose as Carbon Precursor.” Catalysis Today In press. doi: 10.1016/j.cattod.2017.03.056.Search in Google Scholar

Chatterjee, A., and B.L. Deopura. 2002. “Carbon Nanotubes and Nanofibre: An Overview.” Fibers and Polymers 3:134–139.10.1007/BF02912657Search in Google Scholar

Chen, D., K.O. Christensen, E. Ochoa-Fernández, Z. Yu, B. Tøtdal, N. Latorre, A. Monzón, and A. Holmen. 2005. “Synthesis of Carbon Nanofibers: Effects of Ni Crystal Size during Methane Decomposition.” Journal of Catalysis 229:82–96.10.1016/j.jcat.2004.10.017Search in Google Scholar

Chesnokov, V.V., and R.A. Buyanov. 2000. “The Formation of Carbon Filaments upon Decomposition of Hydrocarbons Catalysed by Iron Subgroup Metals and Their Alloys.” Russian Chemical Reviews 69 (7):623–638.10.1070/RC2000v069n07ABEH000540Search in Google Scholar

Chinthaginjala, J.K., K. Seshan, and L. Lefferts. 2007. “Preparation and Application of Carbon-Nanofiber Based Microstructured Materials as Catalyst Supports.” Industrial & Engineering Chemistry Research 46:3968–3978.10.1021/ie061394rSearch in Google Scholar

Corella, J., J. Adanez, and A. Monzón. 1988. “Some Intrinsic Kinetic Equations and Deactivation Mechanisms Leading to Deactivation Curves with a Residual Activity.” Industrial & Engineering Chemistry Research 27 (3):375–381.10.1021/ie00075a002Search in Google Scholar

De Jong, K.P., and J.W. Geus. 2000. “Carbon Nanofibers: Catalytic Synthesis and Applications.” Catalysis Reviews – Science and Engineering 42:481–510.10.1081/CR-100101954Search in Google Scholar

Faugeras, C., A. Nerriere, M. Potemski, A. Mahmood, E. Dujardin, C. Berger, and W.A. De Heer. 2008. “Few-Layer Graphene on SiC, Pyrolitic Graphite, and Graphene: A Raman Scattering Study.” Applied Physics Letters 92:011914.10.1063/1.2828975Search in Google Scholar

Ferrari, A.C., J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, and A.K. Geim. 2006. “Raman Spectrum of Graphene and Graphene Layers.” Physical Review Letters 97:187401.10.1103/PhysRevLett.97.187401Search in Google Scholar PubMed

Gao, L.Z., L. Kiwi-Minsker, and A. Renken. 2008. “Growth of Carbon Nanotubes and Microfibers over Stainless Steel Mesh by Cracking of Methane.” Surface and Coatings Technology 202:3029–3042.10.1016/j.surfcoat.2007.11.006Search in Google Scholar

Geim, A.K. 2009. “Graphene: Status and Prospects.” Science 324:1530–1534.10.1126/science.1158877Search in Google Scholar PubMed

Graf, D., F. Molitor, K. Ensslin, C. Stampfer, A. Jungen, C. Hierold, and L. Wirtz. 2007. “Spatially Resolved Raman Spectroscopy of Single-And Few-Layer Graphene.” Nano Letters 7:238–242.10.1021/nl061702aSearch in Google Scholar PubMed

Hata, K., D.N. Futaba, K. Mizuno, T. Namai, M. Yumura, and S. Iijima. 2004. “Water-assisted highly efficient synthesis of impurity-free single-walled carbon nanotubes.” Science 306 (5700): 1362–1364.10.1126/science.1104962Search in Google Scholar PubMed

Inagaki, M., and L.R. Radovic. 2002. “Nanocarbons.” Carbon 40:2279–2282.10.1016/S0008-6223(02)00204-XSearch in Google Scholar

Jarrah, N.A., J.G. Van Ommen, and L. Lefferts. 2006. “Mechanistic Aspects of the Formation of Carbon-Nanofibers on the Surface of Ni Foam: A New Microstructured Catalyst Support.” Journal of Catalysis 239:460–469.10.1016/j.jcat.2006.02.021Search in Google Scholar

Kaminska, K., J. Lefebvre, D.G. Austing, and P. Finnie. 2007. “Real-Time in Situ Raman Imaging of Carbon Nanotube Growth.” Nanotechnology 18:165707–165713.10.1088/0957-4484/18/16/165707Search in Google Scholar

Kato, T., and R. Hatakeyama. 2010. “Direct Growth of Short Single-Walled Carbon Nanotubes with Narrow-Chirality Distribution by Time-Programmed Plasma Chemical Vapor Deposition.” ACS Nano 4 (12):7395–7400.10.1021/nn102379pSearch in Google Scholar PubMed

Kokai, F., I. Nozaki, T. Okada, A. Koshio, and T. Kuzumaki. 2011. “Efficient Growth of Multi-Walled Carbon Nanotubes by Continuous-Wave Laser Vaporization of Graphite Containing B4C.” Carbon 49 (4):1173–1181.10.1016/j.carbon.2010.11.033Search in Google Scholar

Kong, X.K., C.L. Chen, and Q.W. Chen. 2014. “Doped Graphene for Metal-Free Catalysis.” Chemical Society Reviews 43:2841–2857.10.1039/C3CS60401BSearch in Google Scholar

Latorre, N., F. Cazaña, V. Martínez-Hansen, C. Royo, E. Romeo, and A. Monzón. 2011. “Ni-Co-Mg-Al Catalysts for Hydrogen and Carbonaceous Nanomaterials Production by CCVD of Methane.” Catalysis Today 172:143–151.10.1016/j.cattod.2011.02.038Search in Google Scholar

Latorre, N., F. Cazaña, V. Sebastián, C. Royo, E. Romeo, M.A. Centeno, and A. Monzón. 2016. “Growth of Carbonaceous Nanomaterials over Stainless Steel Foams. Effect of Activation Temperature.” Catalysis Today 273:41–49.10.1016/j.cattod.2016.02.063Search in Google Scholar

Latorre, N., E. Romeo, F. Cazaña, T. Ubieto, C. Royo, J.I. Villacampa, and A. Monzón. 2010a. “Carbon Nanotube Growth by Catalytic Chemical Vapor Deposition: A Phenomenological Kinetic Model.” The Journal of Physical Chemistry C 114:4773–4782.10.1021/jp906893mSearch in Google Scholar

Latorre, N., E. Romeo, J.I. Villacampa, F. Cazaña, C. Royo, and A. Monzón. 2010b. “Kinetics of Carbon Nanotubes Growth on a Ni–Mg–Al Catalyst by CCVD of Methane: Influence of Catalyst Deactivation.” Catalysis Today 154:217–223.10.1016/j.cattod.2010.03.065Search in Google Scholar

Latorre, N., J.I. Villacampa, T. Ubieto, E. Romeo, C. Royo, A. Borgna, and A. Monzon. 2008. “Development of Ni–Al Catalysts for Hydrogen and Carbon Nanofibre Production by Catalytic Decomposition of Methane. Effect of MgO Addition.” Topics in Catalysis 51:158–168.10.1007/s11244-008-9124-xSearch in Google Scholar

Lee, Y., J. Park, Y. Choi, H. Ryu, and H. Lee. 2002. “Temperature-Dependent Growth of Vertically Aligned Carbon Nanotubes in the Range 800− 1100 C.” The Journal of Physical Chemistry B 106:7614–7618.10.1021/jp020488lSearch in Google Scholar

Li, J., E. Croiset, and L. Ricardez-Sandoval. 2015. “Carbon Nanotube Growth: First-Principles-Based Kinetic Monte Carlo Model.” Journal of Catalysis 326:15–25.10.1016/j.jcat.2015.03.010Search in Google Scholar

M S Software. 1995. Statistical Analysis. Salt Lake City, USA: Micromath.Search in Google Scholar

Martínez-Hansen, V., N. Latorre, C. Royo, E. Romeo, E. García-Bordejé, and A. Monzón. 2009. “Development of Aligned Carbon Nanotubes Layers over Stainless Steel Mesh Monoliths.” Catalysis Today 147S:S71–S75.10.1016/j.cattod.2009.07.010Search in Google Scholar

Maruyama, S., R. Kojima, Y. Miyauchi, S. Chiashi, and M. Kohno. 2002. “Low-Temperature Synthesis of High-Purity Single-Walled Carbon Nanotubes from Alcohol.” Chemical Physics Letters 360 (3-4):229–234.10.1016/S0009-2614(02)00838-2Search in Google Scholar

Matatov-Meytal, Y., and M. Sheintuch. 2002. “Catalytic Fibers and Cloths.” Applied Catalysis A 231:1–16.10.1016/S0926-860X(01)00963-2Search in Google Scholar

Mehdipour, H., and K. Ostrikov. 2012. “Kinetics of Low-Pressure, Low-Temperature Graphene Growth: Toward Single-Layer, Single-Crystalline Structure.” ACS Nano 6:10276–10286.10.1021/nn3041446Search in Google Scholar

Meyer, C.I., A.J. Marchi, A. Monzon, and T.F. Garetto. 2009. “Deactivation and Regeneration of Cu/SiO 2 Catalyst in the Hydrogenation of Maleic Anhydride. Kinetic Modeling.” Applied Catalysis A: General 367 (1-2):122–129.10.1016/j.apcata.2009.07.041Search in Google Scholar

Monzon, A., G. Lolli, S. Cosma, S.B. Mohamed, and D.E. Resasco. 2008. “Kinetic Modeling of the SWNT Growth by CO Disproportionation on CoMo Catalysts.” Journal of Nanoscience and Nanotechnology 8:6141–6152.10.1166/jnn.2008.SW21Search in Google Scholar

Monzón, A., E. Romeo, and A. Borgna. 2003. “Relationship between the Kinetic Parameters of Different Catalyst Deactivation Models.” Chemical Engineering Journal 94:19–28.10.1016/S1385-8947(03)00002-0Search in Google Scholar

Mu, C., K. Huang, T. Cheng, H. Wang, H. Yu, and F. Peng. 2016. “Ni Foams Decorated with Carbon Nanotubes as Catalytic Stirrers for Aerobic Oxidation of Cumene.” Chemical Engineering Journal 306:806–815.10.1016/j.cej.2016.08.016Search in Google Scholar

Nebesnyi, A., V. Kotov, A. Sviatenko, D. Filonenko, A. Khovavko, and B. Bondarenko. 2017. “Carbon Nanomaterial Formation on Fresh-Reduced Iron by Converted Natural Gas.” Nanoscale Researcher Letters 12:107–114.10.1186/s11671-017-1882-6Search in Google Scholar

Noda, S., H. Sugime, K. Hasegawa, K. Kakehi, and Y. Shiratori. 2010. “A Simple Combinatorial Method Aiding Research on Single-Walled Carbon Nanotube Growth on Substrates.” Japanese Journal Applications Physical 49 (2):02BA02.10.1143/JJAP.49.02BA02Search in Google Scholar

Novoselov, K.S. 2011. “Nobel Lecture: Graphene: Materials in the Flatland.” Reviews Modern Physical 83:837–849.10.1103/RevModPhys.83.837Search in Google Scholar

Pacheco Benito, S., and L. Lefferts. 2010. “The Production of a Homogeneous and Well-Attached Layer of Carbon Nanofibers on Metal Foils.” Carbon 48:2862–2872.10.1016/j.carbon.2010.04.018Search in Google Scholar

Pérez-Cabero, M., E. Romeo, C. Royo, A. Monzón, A. Guerrero-Ruíz, and I. Rodríguez-Ramos. 2004. “Growing Mechanism of CNTs: A Kinetic Approach.” Journal of Catalysis 224:197–205.10.1016/j.jcat.2004.03.003Search in Google Scholar

Reichelt, E., M.P. Heddrich, M. Jahn, and A. Michaelis. 2014. “Fiber Based Structured Materials for Catalytic Applications.” Applied Catalysis A 476:78–90.10.1016/j.apcata.2014.02.021Search in Google Scholar

Rodríguez, J.C., J.A. Peña, A. Monzón, R. Hughes, and K. Li. 1995. “Kinetic Modelling of the Deactivation of a Commercial Silica-Alumina Catalyst during Isopropylbenzene Cracking.” Chemical Engineering Journal 58:7–13.10.1016/0923-0467(94)02879-FSearch in Google Scholar

Romeo, E., M. Saeys, A. Monzón, and A. Borgna. 2014. “Carbon Nanotube Formation during Propane Decomposition on Boron-Modified Co/Al2O3 Catalysts: A Kinetic Study.” International Journal of Hydrogen Energy 39 (31):18016–18026.10.1016/j.ijhydene.2014.04.168Search in Google Scholar

Sano, N., Y. Hori, S. Yamamoto, and H. Tamon. 2012. “A Simple Oxidation–Reduction Process for the Activation of A Stainless Steel Surface to Synthesize Multi-Walled Carbon Nanotubes and Its Application to Phenol Degradation in Water.” Carbon 50:115–122.10.1016/j.carbon.2011.07.059Search in Google Scholar

Sano, N., S. Yamamoto, and H. Tamon. 2012. “Uniform Synthesis of Multi-Walled Carbon Nanotubes in a Stainless Steel Porous Block.” Carbon 50:5618–5630.10.1016/j.carbon.2012.08.008Search in Google Scholar

Sclove, S 1987. “Application of Model-Selection Criteria to Some Problems in Multivariate Analysis.” Psychometrika 52: 333–343.10.1007/BF02294360Search in Google Scholar

Su, D.S., S. Perathoner, and G. Centi. 2013. “Nanocarbons for the Development of Advanced Catalysts.” Chemical Reviews 113:5782–5816.10.1021/cr300367dSearch in Google Scholar

Takenaka, S., S. Kobayashi, H. Ogihara, and K. Otsuka. 2003. “Ni/SiO2 Catalyst Effective for Methane Decomposition into Hydrogen and Carbon Nanofiber.” Journal of Catalysis 217: 79–87.10.1016/S0021-9517(02)00185-9Search in Google Scholar

Teo, K.B.K., C. Singh, M. Chhowalla, and W.I. Milne. 2003. “Catalytic Synthesis of CNTs and CNFs.” In Encyclopedia of Nanoscience and Nanotechnology, edited by H.S. Nalwa, Vol. 10, 1–22. American Scientific Publishers.Search in Google Scholar

Terrones, M. 2003. “Science and Technology of the Twenty-First Century: Synthesis, Properties, and Applications of Carbon Nanotubes.” Annual Review of Materials Research 33:419–501.10.1146/annurev.matsci.33.012802.100255Search in Google Scholar

Tribolet, P., and L. Kiwi-Minsker. 2005. “Carbon Nanofibers Grown on Metallic Filters as Novel Catalytic Materials.” Catalysis Today 102-103:15–22.10.1016/j.cattod.2005.02.030Search in Google Scholar

Valentini, M., G. Groppi, C. Cristiani, M. Levi, E. Tronconi, and P. Forzatti. 2001. “The Deposition of Γ-Al2O3 Layers on Ceramic and Metallic Supports for the Preparation of Structured Catalysts.” Catalysis Today 69: 307–314.10.1016/S0920-5861(01)00383-2Search in Google Scholar

Villacampa, J.I., C. Royo, E. Romeo, J.A. Montoya, P. Del Angel, and A. Monzón. 2003. “Catalytic Decomposition of Methane over Ni-Al2O3 Coprecipitated Catalysts: Reaction and Regeneration Studies.” Applied Catalysis A 252: 363–383.10.1016/S0926-860X(03)00492-7Search in Google Scholar

Yasaki, S., Y. Yoshino, K. Ihara, and K. Ohkubo, U.S. Patent No. 5, 208 (4 May 1993).Search in Google Scholar

Zhanga, G., S. Sunb, D. Yanga, J.P. Dodeletb, and E. Sachera. 2008. “The Surface Analytical Characterization of Carbon Fibers Functionalized by H2SO4/HNO3 Treatment.” Carbon 46: 196–205.10.1016/j.carbon.2007.11.002Search in Google Scholar

Received: 2017-06-30
Accepted: 2017-09-20
Published Online: 2017-10-14

© 2017 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 28.3.2024 from https://www.degruyter.com/document/doi/10.1515/ijcre-2017-0121/html
Scroll to top button