Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition J.C. Guevara a , J.A. Wang a, *, L.F. Chen a , M.A. Valenzuela a , P. Salas b , A. Garcı ´a-Ruiz c , J.A. Toledo d , M.A. Cortes-Ja ´come d , C. Angeles-Chavez d , O. Novaro e a ESIQIE, Instituto Polite ´cnico Nacional, Col. Zacatenco, Av. Politecnico s/n, 07738 Me ´xico D. F., Mexico b Centro d e Fı ´sica Aplicada y Tecnologı ´a Avanzada, Universidad Nacional Auto ´noma de Me ´xico, Apartado Postal 1-1010, Quere ´taro 76000, Mexico c UPIICSA, Instituto Polite ´cnico Nacional , Te 950 Col. Granjas- Me ´xico, 08400 Me ´xico D.F., Mexico d Programa de Molecular Ingenierı ´a, Instituto Mexicano del Petro ´leo, Eje La ´zaro Ca ´rdenas 152, 07730 Me ´xico D. F., Mexico e Instituto de Fisica, Universidad Nacional Auto ´noma de Me ´xico, A. P. 20-364, 01000 Me ´xico D.F., Mexico a r t i c l e i n f o Article history: Receiv ed 13 October 2009 Receiv ed in revised form 13 January 2010 Accepte d 16 Januar y 2010 Available online 19 February 2010 Keywords: Hydrogen production Methane catalytic decomposition Carbon nanotube Ce-MCM-41 Ni-based catalysts a b s t r a c t For the first time, simultaneou s product ion of hydrog en and nanocarbon via catalytic decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investi- gated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the reaction activity remained almost unchanged during 1400 min steam on time at temper- atures 540, 560 and 580 C, respectively. The methane conversion level over these catalysts reached 60–75% with a 100% selectivity towards hydrogen. TEM observations revealed that most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used catalysts, keeping their exposed surface clean during the test and thus remaining active for continuous reac tio n without obv iou s deactiv ati on. Two kin ds of carbon mat eri als, graphit ic carbon (C g) as major and amorphous carbon ( C A ) as minor were produced in the reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nano- tubes had an average diameter of approximately 30–50 nm and tens micrometers in length, depending on the reaction temperature, reaction time and Ni particle diameter. Four types of carbon nanofibers/nanotubes were detected and their formations greatly depend on the reaction temperature, time on steam and degree of the interaction between the metallic Ni and support. The respective mechanisms of the formation of nanocarbons were postulated and discussed. ª 2010 Professor T. Nejat Veziro glu. Publish ed by Elsevier Ltd. All right s reserve d. 1. Introduction Nowadays, the world is facing two significantly related chal- lenges: an increasing dema nd for new energy and a stringently envi ronmental conce rn. The incr easi ngly envi ronmenta l reg ula tionsrequiretheutili za tion of cleanene rgyin a va ri etyofareas. Hydrogen is such a clean fuel that has received a great attention because of its importance in fuel cell technology, petroleu m refining, food, electronics and metallur gical pro- cessing industries and many other fields [1–4] . Approximately * Corresponding author. Tel.: þ52 55 57296000x55261. E-mail address: [email protected](J.A. Wang). Available at www.sciencedirect.com journal homepage: www.elsevier.com/locate/he international journal of hydrogen energy 35 (2010) 3509–3521 0360-31 99/$ – see front matter ª 2010 Professor T. Nejat Vezirog lu. Publishe d by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2010.01.068
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Ni/Ce-MCM-41 mesostructured catalysts for simultaneousproduction of hydrogen and nanocarbon via
methane decomposition
J.C. Guevaraa, J.A. Wang a,*, L.F. Chen a, M.A. Valenzuela a, P. Salas b, A. Garcı a-Ruiz c, J.A. Toledod, M.A. Cortes-Ja come d, C. Angeles-Chavez d, O. Novaro e
aESIQIE, Instituto Politecnico Nacional, Col. Zacatenco, Av. Politecnico s/n, 07738 Mexico D. F., MexicobCentro de Fı sica Aplicada y Tecnologıa Avanzada, Universidad Nacional Autonoma de Mexico, Apartado Postal 1-1010, Queretaro 76000,
MexicocUPIICSA, Instituto Polite cnico Nacional, Te 950 Col. Granjas-Me xico, 08400 Me xico D.F., MexicodPrograma de Molecular Ingenierıa, Instituto Mexicano del Petro leo, Eje La zaro Ca rdenas 152, 07730 Me xico D. F., Mexicoe Instituto de Fisica, Universidad Nacional Auto noma de Me xico, A. P. 20-364, 01000 Me xico D.F., Mexico
a r t i c l e i n f o
Article history:
Received 13 October 2009
Received in revised form
13 January 2010
Accepted 16 January 2010
Available online 19 February 2010
Keywords:
Hydrogen production
Methane catalytic decomposition
Carbon nanotube
Ce-MCM-41
Ni-based catalysts
a b s t r a c t
For the first time, simultaneous production of hydrogen and nanocarbon via catalytic
decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investi-
gated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the
reaction activity remained almost unchanged during 1400 min steam on time at temper-
atures 540, 560 and 580 C, respectively. The methane conversion level over these catalysts
reached 60–75% with a 100% selectivity towards hydrogen. TEM observations revealed that
most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used
catalysts, keeping their exposed surface clean during the test and thus remaining active for
continuous reaction without obvious deactivation. Two kinds of carbon materials,
graphitic carbon (Cg ) as major and amorphous carbon (CA) as minor were produced in the
reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nano-
tubes had an average diameter of approximately 30–50 nm and tens micrometers in length,
depending on the reaction temperature, reaction time and Ni particle diameter. Four types
of carbon nanofibers/nanotubes were detected and their formations greatly depend on the
reaction temperature, time on steam and degree of the interaction between the metallic Ni
and support. The respective mechanisms of the formation of nanocarbons were postulated
and discussed.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
1. Introduction
Nowadays, the world is facing two significantly related chal-
lenges: an increasing demand for new energy and a stringently
environmental concern. The increasingly environmental
regulations require theutilization of clean energyin a varietyof
areas. Hydrogen is such a clean fuel that has received a great
attention because of its importance in fuel cell technology,
petroleum refining, food, electronics and metallurgical pro-
cessing industries and many other fields [1–4]. Approximately
depended on the reaction temperature and degree of the
interaction between the metallic Ni and the support.
Acknowledgments
The authors thank the financial support from CONACyT-Mexico (Grant No. CONACyT-51007) and Instituto de Ciencia y
Tecnologia de la Ciudad de Mexico (ICyTDF2008) and Instituto
Politecnico Nacional, Mexico (IPN-SIP-20082507 and IPN-SIP-
20090826). J. C. Guevara thanks the Instituto Politecnico
Nacional, Mexico for providing him doctoral scholarship.
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