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Title: In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eV on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [1] ;  [6] ;  [7] ;  [8] ;  [6] ;  [5] ;  [9] ;  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL) (China)
  3. Instituto de Fisica Rosario (IFIR), CONICET (Argentina)
  4. Universidad Central de Venezuela (Venezuela)
  5. Univ. College Cork (Ireland)
  6. Charles Univ., Prague (Czech Republic)
  7. Brookhaven National Lab. (BNL) (United Kingdom)
  8. Univ. Central de Venezuela (Venezuela)
  9. Institute of Catalysis - Madrid (Spain)
Publication Date:
Report Number(s):
BNL-114204-2017-JA
Journal ID: ISSN 1433-7851; R&D Project: CO040; KC0302010
Grant/Contract Number:
SC0012704; CTQ2015-78823-R
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 42; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; Surface Science; methane activation; CO2; Hydrogen production
OSTI Identifier:
1377057
Alternate Identifier(s):
OSTI ID: 1378788

Rodriguez, Jose A., Liu, Zongyuan, Lustemberg, Pablo, Gutierrez, Ramon, Carey, John, Palomino, Robert, Vorohta, Mykhailo, Grinter, David, Ramirez, Pedro, Matolin, Vladimir, Nolan, Michael, Ganduglia-Pirovano, M. Veronica, and Senanayake, Sanjaya. In situ Investigation of Methane Dry Reforming on M-CeO2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature. United States: N. p., Web. doi:10.1002/anie.201707538.
Rodriguez, Jose A., Liu, Zongyuan, Lustemberg, Pablo, Gutierrez, Ramon, Carey, John, Palomino, Robert, Vorohta, Mykhailo, Grinter, David, Ramirez, Pedro, Matolin, Vladimir, Nolan, Michael, Ganduglia-Pirovano, M. Veronica, & Senanayake, Sanjaya. In situ Investigation of Methane Dry Reforming on M-CeO2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature. United States. doi:10.1002/anie.201707538.
Rodriguez, Jose A., Liu, Zongyuan, Lustemberg, Pablo, Gutierrez, Ramon, Carey, John, Palomino, Robert, Vorohta, Mykhailo, Grinter, David, Ramirez, Pedro, Matolin, Vladimir, Nolan, Michael, Ganduglia-Pirovano, M. Veronica, and Senanayake, Sanjaya. 2017. "In situ Investigation of Methane Dry Reforming on M-CeO2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature". United States. doi:10.1002/anie.201707538. https://www.osti.gov/servlets/purl/1377057.
@article{osti_1377057,
title = {In situ Investigation of Methane Dry Reforming on M-CeO2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature},
author = {Rodriguez, Jose A. and Liu, Zongyuan and Lustemberg, Pablo and Gutierrez, Ramon and Carey, John and Palomino, Robert and Vorohta, Mykhailo and Grinter, David and Ramirez, Pedro and Matolin, Vladimir and Nolan, Michael and Ganduglia-Pirovano, M. Veronica and Senanayake, Sanjaya},
abstractNote = {Studies with a series of M-CeO2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO2(111) exhibits the best performance and Cu-CeO2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CHx and COx species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eV on Co(0001) to 0.87 eV on Co2+/CeO2(111), and to only 0.05 eV on Co0/CeO2-x(111). At 700 K, under methane dry reforming conditions, CO2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CHx formed on the Co0/CeO2-x (111) catalyst recombines to yield ethane or ethylene.},
doi = {10.1002/anie.201707538},
journal = {Angewandte Chemie (International Edition)},
number = 42,
volume = 56,
place = {United States},
year = {2017},
month = {8}
}