Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni-CeO2(111) catalysts: an in situ study of C-C and O-H bond scission.
Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Infrared Reflection Absorption Spectroscopy (AP-IRRAS) have been used to elucidate the active sites and mechanistic steps associated with the ethanol steam reforming reaction (ESR) over Ni-CeO2(111) model catalysts. Our results reveal that surface layers of the ceria substrate are both highly reduced and hydroxylated under reaction conditions while the small supported Ni nanoparticles are present as Ni(0)/NixC. A multifunctional, synergistic role is highlighted in which Ni, CeOx and the interface provide an ensemble effect in the active chemistry that leads to H2. Ni(0) is the active phase leading to both C-C and C-H bond cleavage in ethanol and it is also responsible for carbon accumulation. On the other hand, CeOx is important for the deprotonation of ethanol/water to ethoxy and OH intermediates. The active state of CeOx is a Ce(3+)(OH)x compound that results from extensive reduction by ethanol and the efficient dissociation of water. Additionally, we gain an important insight into the stability and selectivity of the catalyst by its effective water dissociation, where the accumulation of surface carbon can be mitigated by the increased presence of surface OH groups. The co-existence and cooperative interplay of Ni(0) and Ce(3+)(OH)x through a metal-support interaction facilitate oxygen transfer, activation of ethanol/water as well as the removal of coke.
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov and Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
Zongyuan
Z
Liu
Faculty of Mathematics and Physics, Charles University in Prague, V Holešovičkách 2, Praha 8, Czech Republic.
Tomáš
T
Duchoň
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov.
Huanru
H
Wang
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov.
David C
DC
Grinter
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov.
Iradwikanari
I
Waluyo
Department of Chemistry, University of Wyoming, Laramine, WY 82071, USA.
Jing
J
Zhou
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
Qiang
Q
Liu
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
Beomgyun
B
Jeong
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
Ethan J
EJ
Crumlin
Faculty of Mathematics and Physics, Charles University in Prague, V Holešovičkách 2, Praha 8, Czech Republic.
Vladimír
V
Matolín
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov.
Dario J
DJ
Stacchiola
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov and Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA.
José A
JA
Rodriguez
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. ssenanay@bnl.gov.
Sanjaya D
SD
Senanayake