共 43 条
Surface Precursors and Reaction Mechanisms for the Thermal Reduction of Graphene Basal Surfaces Oxidized by Atomic Oxygen
被引:92
作者:

Sun, Tao
论文数: 0 引用数: 0
h-index: 0
机构: SISSA, I-34136 Trieste, Italy

Fabris, Stefano
论文数: 0 引用数: 0
h-index: 0
机构:
SISSA, I-34136 Trieste, Italy SISSA, I-34136 Trieste, Italy

Baroni, Stefano
论文数: 0 引用数: 0
h-index: 0
机构: SISSA, I-34136 Trieste, Italy
机构:
[1] SISSA, I-34136 Trieste, Italy
关键词:
HETEROGENEOUS CO2 EVOLUTION;
GRAPHITE SURFACE;
CARBONACEOUS SURFACE;
UNIFIED MECHANISM;
PLASMA OXIDATION;
ADSORPTION;
OXIDE;
MICROSCOPE;
DESORPTION;
STABILITY;
D O I:
10.1021/jp111372k
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
The reduction of graphene oxide surfaces yielding molecular CO/CO2 is studied from first principles using density functional theory. We find that this reaction can proceed exothermically only from surface precursors containing more oxygen atoms than strictly needed to produce CO/CO2 in the gas phase. The calculations show that the lowest-energy configurations of multiple O adsorbates do not involve clustering of epoxy groups (the stable form of O adatoms on graphitic surfaces) but always contain lactone groups either in lactone-ether or in ether-lactone-ether form. We identify these lowest-energy structures as the main reaction precursors. The O adatoms near the lactone group catalyze its gasification to CO/CO2 by reducing the activation energy from above 1.8 eV (from an isolated lactone) to below 0.6 eV (from a lactone-ether). In addition, the residual O adatoms left behind after the lactone gasification minimize the energy of the graphitic products by saturating the dangling bonds of the resulting defective surface. By analyzing defect-free as well as defective surfaces, we identify a common set of concerted reaction mechanisms in which the formation of the gas products and the saturation of the newly formed C vacancies happen simultaneously. The calculated activation energies are in good agreement with the available experimental data.
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页码:4730 / 4737
页数:8
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Univ Paris 06, Inst Mineral & Phys Milieux Condenses, CNRS, IPGP, F-75015 Paris, France
Univ Minnesota, Dept Chem Engn & Mat Sci, Minneapolis, MN 55455 USA CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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de Gironcoli, Stefano
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CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Scuola Int Super Studi Avanzati, SISSA, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Scuola Int Super Studi Avanzati, SISSA, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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Gebauer, Ralph
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h-index: 0
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CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Abdus Salam Int Ctr Theoret Phys, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Gerstmann, Uwe
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h-index: 0
机构:
Univ Paris 06, Inst Mineral & Phys Milieux Condenses, CNRS, IPGP, F-75015 Paris, France CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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h-index: 0
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CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Jozef Stefan Inst, SI-1000 Ljubljana, Slovenia CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Lazzeri, Michele
论文数: 0 引用数: 0
h-index: 0
机构:
Univ Paris 06, Inst Mineral & Phys Milieux Condenses, CNRS, IPGP, F-75015 Paris, France CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Martin-Samos, Layla
论文数: 0 引用数: 0
h-index: 0
机构:
CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Marzari, Nicola
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h-index: 0
机构:
MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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Mazzarello, Riccardo
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Swiss Fed Inst Technol, Dept Chem & Appl Biosci, CH-6900 Lugano, Switzerland CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Paolini, Stefano
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Scuola Int Super Studi Avanzati, SISSA, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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PHB Ecublens, Inst Romand Rech Numer Phys Mat, CH-1015 Lausanne, Switzerland CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Paulatto, Lorenzo
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h-index: 0
机构:
CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Scuola Int Super Studi Avanzati, SISSA, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Sbraccia, Carlo
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h-index: 0
机构:
CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Scandolo, Sandro
论文数: 0 引用数: 0
h-index: 0
机构:
CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Abdus Salam Int Ctr Theoret Phys, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Sclauzero, Gabriele
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h-index: 0
机构:
CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
Scuola Int Super Studi Avanzati, SISSA, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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Smogunov, Alexander
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h-index: 0
机构:
Abdus Salam Int Ctr Theoret Phys, I-34151 Trieste Grignano, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

Umari, Paolo
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h-index: 0
机构:
CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy

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Univ Minnesota, Dept Chem Engn & Mat Sci, Minneapolis, MN 55455 USA
Univ Minnesota, Minnesota Supercomp Inst Adv Computat Res, Minneapolis, MN 55455 USA CNR INFM Democritos Natl Simulat Ctr, I-34100 Trieste, Italy
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