Reaction of Methane with MO                          x                          /CeO                         2                          (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction

Feng Zhang; Siyu Yao; Zongyuan Liu; Ramón A. Gutiérrez; Dimitriy Vovchok; Jiajie Cen; Wenqian Xu; Pedro J. Ramírez; Taejin Kim; Sanjaya D. Senanayake; José A. Rodriguez

doi:10.1021/acs.jpcc.8b09319

Reaction of Methane with MO _x /CeO ₂ (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction

Feng Zhang
, Siyu Yao
, Zongyuan Liu
, Ramón A. Gutiérrez
, Dimitriy Vovchok
, Jiajie Cen
, Wenqian Xu
, Pedro J. Ramírez
, Taejin Kim
, Sanjaya D. Senanayake
, José A. Rodriguez

Materials Science and Engineering

Stony Brook University
Brookhaven National Laboratory
Universidad Central de Venezuela
United States Department of Energy

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

Changes in chemical state and structural transformations occurring in a series of MO _x /CeO ₂ (M = Cu, Ni and Fe) powder catalysts upon reaction with methane were investigated using in situ time-resolved X-ray diffraction (TR-XRD), ex situ X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS shows the presence of adsorbed CH _x and CO _x species after exposing the powder catalysts to methane at room temperature. Temperature-programmed reduction (TPR) measurements point to reaction of the samples with methane and formation of CO, CO ₂ , and H ₂ O gas at temperatures as low as 100 °C. The TR-XRD results show that all of the transition-metal oxides in the as-prepared catalysts can be reduced to their metallic phase during the CH ₄ -TPR process with the ceria support undergoing significant reduction from surface to bulk, yet the reduction temperature varies for different MO _x /CeO ₂ samples. Among these samples, CuO _x /CeO ₂ shows the lowest reduction temperature (below 260 °C) for both the oxide overlayer and the ceria support. The NiO _x /CeO ₂ and CoO _x /CeO ₂ powder catalysts also activate CH ₄ at relatively low temperatures (below 350 °C), and the oxide overlayers undergo NiO → Ni and Co ₃ O ₄ → CoO → Co transformations. In the case of FeO _x /CeO ₂ , a series of complex changes in chemical state is observed for the oxide overlayer, Fe ₂ O ₃ → Fe ₃ O ₄ → FeO → Fe → Fe ₃ C. The ceria support of the three MO _x /CeO ₂ (M = Cu, Ni, and Fe) samples undergoes severe reduction and forms Ce ₂ O ₃ at high temperature (>650 °C) during the CH ₄ -TPR reaction. The in situ TR-XRD results highlight a rich and complex chemistry for methane on these MO _x /CeO ₂ mixed oxide systems.

Original language	English
Pages (from-to)	28739-28747
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	122
Issue number	50
DOIs	https://doi.org/10.1021/acs.jpcc.8b09319
State	Published - Dec 20 2018

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10.1021/acs.jpcc.8b09319

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Zhang, F., Yao, S., Liu, Z., Gutiérrez, R. A., Vovchok, D., Cen, J., Xu, W., Ramírez, P. J., Kim, T., Senanayake, S. D., & Rodriguez, J. A. (2018). Reaction of Methane with MO _x /CeO ₂ (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction. Journal of Physical Chemistry C, 122(50), 28739-28747. https://doi.org/10.1021/acs.jpcc.8b09319

@article{a2bd6ce0a0c24b569572bbf7b07d236f,

title = "Reaction of Methane with MO x /CeO 2 (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction",

abstract = " Changes in chemical state and structural transformations occurring in a series of MO x /CeO 2 (M = Cu, Ni and Fe) powder catalysts upon reaction with methane were investigated using in situ time-resolved X-ray diffraction (TR-XRD), ex situ X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS shows the presence of adsorbed CH x and CO x species after exposing the powder catalysts to methane at room temperature. Temperature-programmed reduction (TPR) measurements point to reaction of the samples with methane and formation of CO, CO 2 , and H 2 O gas at temperatures as low as 100 °C. The TR-XRD results show that all of the transition-metal oxides in the as-prepared catalysts can be reduced to their metallic phase during the CH 4 -TPR process with the ceria support undergoing significant reduction from surface to bulk, yet the reduction temperature varies for different MO x /CeO 2 samples. Among these samples, CuO x /CeO 2 shows the lowest reduction temperature (below 260 °C) for both the oxide overlayer and the ceria support. The NiO x /CeO 2 and CoO x /CeO 2 powder catalysts also activate CH 4 at relatively low temperatures (below 350 °C), and the oxide overlayers undergo NiO → Ni and Co 3 O 4 → CoO → Co transformations. In the case of FeO x /CeO 2 , a series of complex changes in chemical state is observed for the oxide overlayer, Fe 2 O 3 → Fe 3 O 4 → FeO → Fe → Fe 3 C. The ceria support of the three MO x /CeO 2 (M = Cu, Ni, and Fe) samples undergoes severe reduction and forms Ce 2 O 3 at high temperature (>650 °C) during the CH 4 -TPR reaction. The in situ TR-XRD results highlight a rich and complex chemistry for methane on these MO x /CeO 2 mixed oxide systems.",

author = "Feng Zhang and Siyu Yao and Zongyuan Liu and Guti{\'e}rrez, \{Ram{\'o}n A.\} and Dimitriy Vovchok and Jiajie Cen and Wenqian Xu and Ram{\'i}rez, \{Pedro J.\} and Taejin Kim and Senanayake, \{Sanjaya D.\} and Rodriguez, \{Jos{\'e} A.\}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = dec,

day = "20",

doi = "10.1021/acs.jpcc.8b09319",

language = "English",

volume = "122",

pages = "28739--28747",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

number = "50",

}

Zhang, F, Yao, S, Liu, Z, Gutiérrez, RA, Vovchok, D, Cen, J, Xu, W, Ramírez, PJ, Kim, T, Senanayake, SD & Rodriguez, JA 2018, 'Reaction of Methane with MO _x /CeO ₂ (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction', Journal of Physical Chemistry C, vol. 122, no. 50, pp. 28739-28747. https://doi.org/10.1021/acs.jpcc.8b09319

Reaction of Methane with MO _x /CeO ₂ (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction. / Zhang, Feng; Yao, Siyu; Liu, Zongyuan et al.
In: Journal of Physical Chemistry C, Vol. 122, No. 50, 20.12.2018, p. 28739-28747.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Reaction of Methane with MO x /CeO 2 (M = Fe, Ni, and Cu) Catalysts

T2 - In Situ Studies with Time-Resolved X-ray Diffraction

AU - Zhang, Feng

AU - Yao, Siyu

AU - Liu, Zongyuan

AU - Gutiérrez, Ramón A.

AU - Vovchok, Dimitriy

AU - Cen, Jiajie

AU - Xu, Wenqian

AU - Ramírez, Pedro J.

AU - Kim, Taejin

AU - Senanayake, Sanjaya D.

AU - Rodriguez, José A.

PY - 2018/12/20

Y1 - 2018/12/20

N2 - Changes in chemical state and structural transformations occurring in a series of MO x /CeO 2 (M = Cu, Ni and Fe) powder catalysts upon reaction with methane were investigated using in situ time-resolved X-ray diffraction (TR-XRD), ex situ X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS shows the presence of adsorbed CH x and CO x species after exposing the powder catalysts to methane at room temperature. Temperature-programmed reduction (TPR) measurements point to reaction of the samples with methane and formation of CO, CO 2 , and H 2 O gas at temperatures as low as 100 °C. The TR-XRD results show that all of the transition-metal oxides in the as-prepared catalysts can be reduced to their metallic phase during the CH 4 -TPR process with the ceria support undergoing significant reduction from surface to bulk, yet the reduction temperature varies for different MO x /CeO 2 samples. Among these samples, CuO x /CeO 2 shows the lowest reduction temperature (below 260 °C) for both the oxide overlayer and the ceria support. The NiO x /CeO 2 and CoO x /CeO 2 powder catalysts also activate CH 4 at relatively low temperatures (below 350 °C), and the oxide overlayers undergo NiO → Ni and Co 3 O 4 → CoO → Co transformations. In the case of FeO x /CeO 2 , a series of complex changes in chemical state is observed for the oxide overlayer, Fe 2 O 3 → Fe 3 O 4 → FeO → Fe → Fe 3 C. The ceria support of the three MO x /CeO 2 (M = Cu, Ni, and Fe) samples undergoes severe reduction and forms Ce 2 O 3 at high temperature (>650 °C) during the CH 4 -TPR reaction. The in situ TR-XRD results highlight a rich and complex chemistry for methane on these MO x /CeO 2 mixed oxide systems.

AB - Changes in chemical state and structural transformations occurring in a series of MO x /CeO 2 (M = Cu, Ni and Fe) powder catalysts upon reaction with methane were investigated using in situ time-resolved X-ray diffraction (TR-XRD), ex situ X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS shows the presence of adsorbed CH x and CO x species after exposing the powder catalysts to methane at room temperature. Temperature-programmed reduction (TPR) measurements point to reaction of the samples with methane and formation of CO, CO 2 , and H 2 O gas at temperatures as low as 100 °C. The TR-XRD results show that all of the transition-metal oxides in the as-prepared catalysts can be reduced to their metallic phase during the CH 4 -TPR process with the ceria support undergoing significant reduction from surface to bulk, yet the reduction temperature varies for different MO x /CeO 2 samples. Among these samples, CuO x /CeO 2 shows the lowest reduction temperature (below 260 °C) for both the oxide overlayer and the ceria support. The NiO x /CeO 2 and CoO x /CeO 2 powder catalysts also activate CH 4 at relatively low temperatures (below 350 °C), and the oxide overlayers undergo NiO → Ni and Co 3 O 4 → CoO → Co transformations. In the case of FeO x /CeO 2 , a series of complex changes in chemical state is observed for the oxide overlayer, Fe 2 O 3 → Fe 3 O 4 → FeO → Fe → Fe 3 C. The ceria support of the three MO x /CeO 2 (M = Cu, Ni, and Fe) samples undergoes severe reduction and forms Ce 2 O 3 at high temperature (>650 °C) during the CH 4 -TPR reaction. The in situ TR-XRD results highlight a rich and complex chemistry for methane on these MO x /CeO 2 mixed oxide systems.

UR - https://www.scopus.com/pages/publications/85058954482

U2 - 10.1021/acs.jpcc.8b09319

DO - 10.1021/acs.jpcc.8b09319

M3 - Article

AN - SCOPUS:85058954482

SN - 1932-7447

VL - 122

SP - 28739

EP - 28747

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 50

ER -

Zhang F, Yao S, Liu Z, Gutiérrez RA, Vovchok D, Cen J et al. Reaction of Methane with MO _x /CeO ₂ (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction. Journal of Physical Chemistry C. 2018 Dec 20;122(50):28739-28747. doi: 10.1021/acs.jpcc.8b09319

Reaction of Methane with MO _x /CeO ₂ (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction

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