In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO<sub>2</sub> Catalyst: Importance of Strong Metal–Support Interactions for the Cleavage of O–H Bonds

Angewandte Chemie - International Edition - Tập 54 Số 13 - Trang 3917-3921 - 2015
Javier Carrasco1,2, David López‐Durán1,2,3, Zongyuan Liu4,5, Tomáš Duchoň6, Jonathan P. Evans7, Sanjaya D. Senanayake4, Ethan J. Crumlin8, Vladimı́r Matolín6, José A. Rodríguez4,5,9,10, M. V. Ganduglia-Pirovano2,9,10
1CIC Energigune, Albert Einstein 48, 01510 Miñano, Álava (Spain)
2Instituto de Catálisis y Petroleoquímica, CSIC, C/Marie Curie, 2. 28049 Madrid, Spain
3Present address: Departamento de Química Analítica, Química Física e Ingeniería Química, Universidad de Alcalá, 28871 Alcalá de Henares, Madrid (Spain)
4Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973 USA
5Dept. of Chem., SUNY, Stony Brook, NY 11749 (USA)
6Faculty of Mathematics and Physics, Charles University, V Holešovičách 2, Praha 8 (Czech Republic)
7Facultad de Ciencias, Universidad Central de Venezuela, Caracas 1020A (Venezuela)
8Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
9José A. Rodríguez, Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973 (USA)
10M. Verónica Ganduglia-Pirovano, Instituto de Catálisis y Petroleoquímica, CSIC, C/Marie Curie 2, 28049 Madrid (Spain)

Tóm tắt

AbstractWater dissociation is crucial in many catalytic reactions on oxide‐supported transition‐metal catalysts. Supported by experimental and density‐functional theory results, the effect of the support on OH bond cleavage activity is elucidated for nickel/ceria systems. Ambient‐pressure O 1s photoemission spectra at low Ni loadings on CeO2(111) reveal a substantially larger amount of OH groups as compared to the bare support. Computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO2(111) compared with pyramidal Ni4 particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni2+ species by accommodating electrons in localized f‐states. The fast dissociation of water on Ni/CeO2 has a dramatic effect on the activity and stability of this system as a catalyst for the water‐gas shift and ethanol steam reforming reactions.

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Angewandte Chemie - International Edition

Tập 54 Số 13

3917-3921

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