Mechanism of CH4 Dry Reforming by Pulse Microcalorimetry: Metal Nanoparticles on Perovskite/Fluorite Supports with High Oxygen Mobility
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Thermochimica Acta
ISSN: 0040-6031
, E-ISSN: 1872-762X
|
| Output data |
Year: 2013,
Volume: 567,
Pages: 27- 34
Pages count
: 8
DOI:
10.1016/j.tca.2013.01.034
|
| Tags |
Bonding strength and reactivity of oxygen species, CH4 dry reforming, Metal clusters, Perovskite and fluorite oxide supports, Pulse microcalorimetry, Redox mechanism |
| Authors |
Sadykov Vladislav
1,2
,
Rogov Vladimir
1,2
,
Ermakova Eugenia
2
,
Arendarsky Dmitry
1
,
Mezentseva Natalia
1,2
,
Alikina Galina
1
,
Sazonova Natalia
1
,
Bobin Aleksey
1
,
Pavlova Svetlana
1
,
Schuurman Yves
3
,
Mirodatos Claude
3
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis SB RAS
|
| 2 |
Novosibirsk State University
|
| 3 |
Institute of Researches on Catalysis and Environment in Lyon
|
|
Funding (4)
|
1
|
European Commission
|
228953 FP7-NMP-2008-LARGE-2 OCMOL
|
|
2
|
Russian Foundation for Basic Research
|
09-03-93112
|
|
3
|
French Embassy in Moscow
|
|
|
4
|
The Ministry of Education and Science of the Russian Federation
|
|
The mechanism of CH4 dry reforming on Pt, Ru, Ni, Ni + Ru-supported perovskite (PrFeOx, LaPrMnCrOx) or fluorite (LnCeZrOx) oxides was studied using a Setaram Sensys DSC TG calorimeter and a pulse kinetic installation. For catalysts in the steady-state, CH4 and CO2 transformation in separate pulses proceeds with the rate and products selectivity equal to that in mixed CO2 + CH4 pulses. Heat effects of separate stages correspond to CH4 oxidation into syngas by strongly bound bridging oxygen forms of support (heat of adsorption up to 650 kJ mol−1 O2 for fluorites and ∼500 kJ mol−1 O2 for perovskites) and their replenishment by CO2 dissociation, respectively. These features demonstrate a step-wise red-ox (Mars-van-Crevelen) mechanism of CH4 dry reforming. Fast oxygen transfer from the sites of oxide support to the metal/oxide interface provides required conjugation of stages.