Abstract
Starting from an overview of general concepts in Fischer–Tropsch synthesis, this perspective article focuses on relevant theoretical works based on density functional theory (DFT) dealing with cobalt based Fischer–Tropsch (FT) catalysis. Our bibliographic analysis highlights key scientific questions in a challenging field for research and industry. Starting from the historical and empirical concepts, we discuss how recent DFT studies give insights into the catalyst structure, the FT reaction mechanisms and the deactivation pathways. There is still no clear consensus within the scientific community about the FT reaction mechanism. Some authors propose that the first elementary step in the FT synthesis consists on CO dissociation taking place at the steps of the cobalt active phase (carbide mechanism) while some others suggest that this molecule is hydrogenated prior to its dissociation no matter the structure of the active site (insertion mechanism). As for the crucial deactivation problem, according to the computed thermodynamic properties presented by some publications, the catalyst oxidation does not seem to play a major role in its deactivation process. By contrast, the interaction of C addatoms with the Co active phase can have a strong influence on the catalyst reactivity and selectivity, through a series of structural rearrangements: the formation of various more or less unsaturated hydrocarbon molecules (such as polyaromatic rings) and the formation of a surface carbide phase. However, the impact of these phenomena on the reactivity and selectivity of the catalyst remain to be investigated in the future.
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Sabatier P, Senderens JB (1902) C R Acad Sci Paris 134:514
Mittasch A, Schneider C (1916) US Patent 1,201,850
Fischer F, Tropsch H (1926) Brennstoff-Chemie 7:97
Dry ME (1996) Appl Catal A 138:319
Saib AM, Moodley DJ, Ciobîcă IM, Hauman MM, Sigwebela BH, Weststrate CJ, Niemantsverdriet JW, van de Loosdrecht J (2010) Catal Today 154:271
van Steen E, Claeys M (2008) Chem Eng Technol 31:655
Casci JL, Lok CM, Shannon MD (2009) Catal Today 145:38
Adesina AA (1996) Appl Catal A 138:345
Van der Laan GP, Beenackers A (1999) Catal Rev Sci Eng 41:255
Overett MJ, Hill RO, Moss JR (2000) Coord Chem Rev 206:581
Voillequin B, Luck F (2011) Actual Chim 350:16
Anderson RB, Köbel-Engelhardt H, Ralek M (1984) The Fischer-Tropsch Synthesis. Academic Press Inc, Orlando
de Klerk A (2011) Fischer-Tropsch Refining. Wiley-VCH Verlag GmbH & Co KGaA, Weinheim
van Santen RA, Ghouri MM, Shetty S, Hensen EMH (2011) Catal Sci Technol 1:891
van Santen RA, Ciobîcă IM, van Steen E, Ghouri MM (2011) Advances in catalysis, vol 54. Elsevier Academic Press Inc, San Diego, p 127
Kohn W, Sham LJ (1965) Phys Rev 140:A1133
Hafner J (2010) J Phys Condens Matter 22:384205
Hafner J (2010) Nat Mater 9:690
de Klerk A (2011) Fischer-Tropsch Refining. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, p 73
Vannice MA (1975) J Catal 37:449
Dry ME (2002) J Chem Technol Biotechnol 77:43
Kummer JT, De Witt TW, Emmett PH (1948) J Am Chem Soc 70:3632
Storch HH, Golumbic N, Anderson RB (1951) The Fischer-Tropchs and Related Syntheses. Wiley, New York
Fahey DR (1981) J Am Chem Soc 103:136
Roginski SZ (1965) In: 3rd International Congress on Catalysis. North-Holland Publishing Co., p 939
Pichler H, Schulz H (1970) Chem Eng Tech 42:1162
Henrici-Olivé G, Olivé S (1976) Angew Chem Int Ed Engl 15:136
Ponec V (1978) Catal Rev Sci Eng 14:153
Ponec V (1978) Catal Rev Sci Eng 18:151
Brady RC, Pettit R (1980) J Am Chem Soc 102:6181
Brady RC, Pettit R (1981) J Am Chem Soc 103:1287
Maitlis PM (1989) Pure Appl Chem 61:1747
Watwe RM, Cortright RD, Nørskov JK, Dumesic JA (2000) J Phys Chem B 104:2299
Sanchez-Escribano V, Larrubia Vargas MA, Finocchio E, Busca G (2007) Appl Catal A 316:68
Gaube J, Klein HF (2010) Appl Catal A 374:120
Gaube J, Klein HF (2008) Appl Catal A 350:126
Gaube J, Klein HF (2007) J Mol Catal A Chem 283:60
Zhuo MK, Tan KF, Borgna A, Saeys M (2009) J Phys Chem C 113:8357
Bundhoo A, Schweicher J, Frennet A, Kruse N (2009) Journal Phys Chem C 113:10731
Ojeda M, Nabar R, Nilekar AU, Ishikawa A, Mavrikakis M, Iglesia E (2010) J Catal 272:287
Inderwildi RO, Jenkins SJ, King DA (2008) J Phys Chem C 112:1305
Weststrate CJ, Gericke HJ, Verhoeven MWGM, Ciobîcă IM, Saib AM, Niemantsverdriet JW (2010) J Phys Chem Lett 1:1767
Schweicher J, Bundhoo A, Frennet A, Kruse N, Daly H, Meunier FdrC (2010) J Phys Chem C 114:2248
Markvoort AJ, van Santen RA, Hilbers PAJ, Hensen EJM (2012) Angew Chem Int Ed Engl 51:8904
Wilson J, de Groot C (1995) J Phys Chem 99:7860
Hermann K (2009) In: van Santen RA, Sautet P (eds) Computational methods in catalysis and materials science. Wiley-VCH Verlag GmbH & Co. KGA, Weinheim, p 265
Cheng J, Gong XQ, Hu P, Lok CM, Ellis P, French S (2008) J Catal 254:285
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2008) J Catal 257:221
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2008) J Phys Chem C 112:9464
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2008) J Phys Chem C 112:6082
Gong XQ, Raval R, Hu P (2004) Surf Sci 562:247
Gong XQ, Raval R, Hu P (2004) Mol Phys 102:993
Gong XQ, Raval R, Hu P (2005) J Chem Phys 122:024711
Andersson MP, Abild-Pedersen F, Remediakis IN, Bligaard T, Jones G, Engbæk J, Lytken O, Horch S, Nielsen JH, Sehested J, Rostrup-Nielsen JR, Nørskov JK, Chorkendorff I (2008) J Catal 255:6
Shetty S, van Santen RA (2011) Catal Today 171:168
Bligaard T, Nørskov JK, Dahl S, Matthiesen J, Christensen CH, Sehested J (2004) J Catal 224:206
Cao XM, Burch R, Hardacre C, Hu P (2011) Catal Today 165:71
Chizallet C, Bonnard G, Krebs E, Bisson L, Thomazeau C, Raybaud P (2011) J Phys Chem C 115:12135
van Helden P, Van Den Berg JA, Weststrate KJ (2012) ACS Catal 2:1097
Liu ZP, Hu P (2003) J Am Chem Soc 125:1958
Cheng J, Song T, Hu P, Lok CM, Ellis P, French S (2008) J Catal 255:20
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2009) J Phys Chem C 113:8858
Cheng J, Hu P (2008) J Am Chem Soc 130:10868
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2009) Surf Sci 603:2752
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2010) Top Catal 53:326
Kapur N, Hyun J, Shan B, Nicholas JB, Cho K (2010) J Phys Chem C 114:10171
van Berge PJ, Everson RC (1997) Stud Surf Sci Catal 107:207
Bartholomew CH (2001) Appl Catal A 212:17
Lahtinen J, Kantola P, Jaatinen S, Habermehl-Cwirzen K, Salo P, Vuorinen J, Lindroos M, Pussi K, Seitsonen A (2005) Surf Sci 599:113
Ma SH, Jiao ZY, Yang ZX (2010) Surf Sci 604:817
Curulla-Ferre D, Govender A, Bromfield TC, Niemantsverdriet JW (2006) J Phys Chem B 110:13897
Nieskens DLS, Curulla Ferré D, Niemantsverdriet JW (2005) ChemPhysChem 6:1293
de Klerk A (2011) Fischer-Tropsch Refining. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, p 23
Agrawal PK, Katzer JR, Manogue WH (1981) J Catal 69:312
Schweiger H, Raybaud P, Toulhoat H (2002) J Catal 212:33
van Steen E, Claeys M, Dry ME, van de Loosdrecht J, Viljoen EL, Visagie JL (2005) J Phys Chem B 109:3575
Swart JCW (2008) PhD thesis, University of Cape Town, Cape Town
Liu ZP, Hu P, Lee MH (2003) J Chem Phys 119:6282
van de Loosdrecht J, Bazhinimaev B, Dalmon JA, Niemantsverdriet JW, Tsybulya SV, Saib AM, van Berge PJ, Visagie JL (2007) Catal Today 123:293
Moodley D (2008) PhD thesis, Eindhoven University of Technology, Eindhoven
Moodley DJ, Saib AM, van de Loosdrecht J, Welker-Nieuwoudt CA, Sigwebela BH, Niemantsverdriet JW (2011) Catal Today 171:192
Andersson JM, Wallin E, Chirita V, Lünger EP, Helmersson U (2005) Phys Rev B 71:014101
Tsakoumis NE, Rønning M, Borg Ø, Rytter E, Holmen A (2010) Catal Today 154:162
Moodley DJ, van de Loosdrecht J, Saib AM, Overett MJ, Datye AK, Niemantsverdriet JW (2009) Appl Catal A 354:102
Tan KF, Xu J, Chang J, Borgna A, Saeys M (2010) J Catal 274:121
Sellmer C, Decker S, Kruse N (1998) Catal Lett 52:131
Peña D, Nunsa N, Griboval-Constanta A, Khodakova AY, Lecocq V, Diehl F (2012) SynFuel, Munich, Germany, Submitted
Nakamura J, Tanaka K, Toyoshima I (1987) J Catal 108:55
Nolan PE, Lynch DC, Cutler AH (1998) J Phys Chem B 102:4165
Barbier A, Tuel A, Arcon I, Kodre A, Martin GA (2001) J Catal 200:106
Swart JCW, Ciobîcă LM, van Santen RA, van Steen E (2008) J Phys Chem C 112:12899
Swart JCW, van Steen E, Ciobîcă IM, van Santenc RA (2009) Phys Chem Chem Phys 11:803
Bian G, Nanba T, Koizumi N, Yamada M (2002) J Mol Catal A Chem 178:219
Bian GZ, Fujishita N, Mochizuki T, Ning WS, Yamada M (2003) Appl Catal A 252:251
Ducreux O, Rebours B, Lynch J, Roy-Auberger M, Bazin D (2009) OGST 64:49
Karaca H, Hong JP, Fongarland P, Roussel P, Griboval-Constant A, Lacroix M, Hortmann K, Safonova OV, Khodakov AY (2010) Chem Commun 46:788
Pan ZD, Bukur DB (2011) Appl Catal A 404:74
Sadeqzadeh M, Karaca H, Safonova OV, Fongarland P, Chambrey S, Roussel P, Griboval-Constant A, Lacroix M, Curulla-Ferre D, Luck F, Khodakov AY (2011) Catal Today 164:62
Ducreux O, Lynch J, Rebours B, Roy M, Chaumette P (1998) Natural Gas Conversion V, p 125
Enache DI, Rebours B, Roy-Auberger M, Revel R (2002) J Catal 205:346
Cheng J, Hu P, Ellis P, French S, Kelly G, Lok CM (2010) J Phys Chem C 114:1085
Sautet P, Cinquini F (2010) ChemCatChem 2:636
Li BH, Zhang QJ, Chen LA, Cui P, Pan XQ (2010) Phys Chem Chem Phys 12:7848
Ciobîcă IM, van Santen RA, van Berge PJ, van de Loosdrecht J (2008) Surf Sci 602:17
Klink C, Stensgaard I, Besenbacher F, Lagsgaard E (1995) Surf Sci 342:250
Ducreux O, Lynch J, Marion MC, Roy M (2000) Abstr Pap Am Chem S 219:U259
Raucoules R, de Bruin T, Adamo C, Raybaud P (2012) Organometallics 30:3911
Shetty S, Jansen APJ, van Santen RA (2009) J Am Chem Soc 131:12874
Acknowledgments
We would like to express our gratitude to Professor Norbert Kruse, from the Free University of Brussels, for fruitful scientific discussions.
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Corral Valero, M., Raybaud, P. Cobalt Catalyzed Fischer–Tropsch Synthesis: Perspectives Opened by First Principles Calculations. Catal Lett 143, 1–17 (2013). https://doi.org/10.1007/s10562-012-0930-1
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DOI: https://doi.org/10.1007/s10562-012-0930-1