Theoretical Study on the Activation of Ammonia by Ni atom

被引：0

作者：

Xie Jun ^{[1
]}

Qin Song ^{[1
]}

Tang Dianyong ^{[1
]}

Hu Changwei ^{[1
]}

机构：

[1] Sichuan Univ, Coll Chem, Minst Educ, Key Lab Green Chem & Technol, Chengdu 610064, Peoples R China

来源：

ACTA CHIMICA SINICA | 2010年 / 68卷 / 10期

关键词：

N - H bond activation; Ni catalyst; density functional theory; quantum theory of atom-in-molecule (QTAIM); TRANSITION-METAL CATIONS; MATRIX-ISOLATION; NH3; CATALYSTS; BOND; SC+;

D O I：

暂无

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The activation of ammonia by Ni atom was investigated at the UB3LYP/6-311++G(3df,3pd) level All the stationary points were analyzed by the Quantum Theory of Atom-In-Molecule (QTAIM). The computational results indicate that the singlet state contains two reaction channels, while the triplet includes only one reaction channel. The free energy barrier for the activation of the first N-H bond is 100.86 kJ/mol at 298.15 K and 101.325 kPa, thus it is feasible at room temperature. However, the activation of the second N-H to form the H2NiNH intermediate is very difficult, because its energy barrier is higher than 200 kJ/mol. Therefore, Ni is a good catalyst for the activation of NH3 to form NH2 radical.

引用

页码：969 / 974

页数：6

共 23 条

[1] A study of the mechanism of selective conversion of ammonia to nitrogen on Ni/γ-Al2O3 under strongly oxidising conditions
Amblard, M
Burch, R
Southward, BWL
[J]. CATALYSIS TODAY, 2000, 59 (3-4) : 365 - 371
[2] Amination of benzene in the presence of ammonia using a Group VIII metal supported on a carrier as catalyst
Becker, J
Holderich, WF
[J]. CATALYSIS LETTERS, 1998, 54 (03) : 125 - 128
[3] THEORETICAL-STUDY OF THE ACTIVATION OF THE N-H BOND IN AMMONIA BY 2ND ROW TRANSITION-METAL ATOMS
BLOMBERG, MRA
SIEGBAHN, EM
SVENSSON, M
[J]. INORGANIC CHEMISTRY, 1993, 32 (20) : 4218 - 4225
[4] Ammonia activation by early transition metal atoms (Sc, Ti, and V). Matrix isolation infrared spectroscopic and density functional theory studies
Chen, MH
Lu, H
Dong, J
Miao, L
Zhou, MF
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (47): : 11456 - 11464
[5] Theoretical study of two-state reactivity of transition metal cations: The "difficult" case of iron ion interacting with water, ammonia, and methane
Chiodo, S
Kondakova, O
Michelini, MD
Russo, N
Sicilia, E
Irigoras, A
Ugalde, JM
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (06): : 1069 - 1081
[6] Reaction of bare VO+ and FeO+ with ammonia:: A theoretical point of view
Chiodo, S
Kondakova, O
Michelini, MD
Russo, N
Sicilia, E
[J]. INORGANIC CHEMISTRY, 2003, 42 (26) : 8773 - 8782
[7] The thermal chemistry of ammonia on Ni(110)
Chrysostomou, D
Flowers, J
Zaera, F
[J]. SURFACE SCIENCE, 1999, 439 (1-3) : 34 - 48
[8] AMMONIA ACTIVATION BY CO+, NI+, AND CU+ - M+-NH2 BOND-ENERGIES AND M+=NH3 ADDUCT LIFETIMES
CLEMMER, DE
ARMENTROUT, PB
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (08): : 3084 - 3090
[9] AMMONIA ACTIVATION BY V+ - ELECTRONIC AND TRANSLATIONAL ENERGY-DEPENDENCE
CLEMMER, DE
SUNDERLIN, LS
ARMENTROUT, PB
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (01): : 208 - 217
[10] AMMONIA ACTIVATION BY SC+ AND TI+ - ELECTRONIC AND TRANSLATIONAL ENERGY-DEPENDENCE
CLEMMER, DE
SUNDERLIN, LS
ARMENTROUT, PB
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (07): : 3008 - 3015

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