A DFT Study of NO Reduction Promoted by Gold Cluster

Scientific Journal of Frontier Chemical Development
SJFCD
NO
255300
Au4 Au4 NO/H2 Au4+

+
Au4 NO/H2 H2 H2 H NO OH ,
H2O N2O H2
H2 NO
NO
A DFT Study of NO Reduction Promoted by Gold Cluster

Changqing Guo
Shandong Silk Textile Vocational College, Zibo, China, 255300
hxwyy2005@126.com
Abstract While nanoscale gold particles show exceptional catalytic activity towards NO reduction, not much is known about the
detailed reaction mechanism and the influence of charge state of Au nanoparticles on the reactivity. We here report a systematic
theoretical study by carrying out density functional theory calculations for NO reduction promoted by Au4+ and Au4, which represent
two simplest prototypes of Au nanoparticles with different charge states. In all cases, it is found that the catalytic cycle proceeds via
the complexes of Au-H with NO and involves two sequential elementary steps: the rupture of the H-H bond in H2 and the formation
of H2O and N2O molecule. The calculated results show that the cationic cluster is generally more active than the neutral cluster,
indicating that the activity of Au cluster towards NO reduction is attributable to the concentration of positive charges on the cluster.
The present theoretical study rationalizes the early experimental findings well and enriches our understanding of the reduction of NO
on the Au cluster.
Key words Gold catalyst; Density functional theory; NO reduction
100 :
NO NO H2
H2 NO
NO
NO + H2 N2 ( NH3N2O) + H2O
SJFCD Vol.1 No.1 Dec. 2011 pp.1-8 www.sjfcd.org 2011 American V-King Scientific Publishing, LTD
-1-
SJFCD
Galvagno [1] Au/SiO2, Au/Al2O3, Au/MgO

H2 NO 150
[2] ()
[3-5]Ichikawa [6] NaY
H2 NO
, NO H2 NO
H2 H NO OH H2O N2O NO
NO N-O
NO (DFT)
Wang [3] DFT
H2 NO N 2O Au4+ Au4 NO
[7]
[8] H2 NO
H2 NO
NO
1.1
Gaussion 03[9], DFT UB3LYP [10] Los Alamos LANL2DZ[11-12]
[13] 6-311++G (d, p)
,()
Peng Schlegel [14](STQN)
(IRC)
, ,
,
1.2
1.2.1
NO 1.148 1.151 [15]N 2O N-N N-O

1.126 1.185 1.129 1.118 [16],
Au4 67.28 191.50 kcal mol -159.96 2.31 198.07 kcal
mol -1[17,18],
B3LYP/Lanl2DZ NO Au4+ Au4 1NO 5
N Au4z(NO) (z = 0, +1) Au4z NO N O
-2-
SJFCD
FOP NO HOMO LUMO

NO LUMO Au4 Au4+ HOMO NO N Au4z(z=0, +1)
1
NO H2 (Ebs)
Eb = Emol + E Au EAu-mol
E mol E Au E Au-mol
Eb Au4+ > Au4 NO H2
6s
(1.151)
(1.118)
1.126
0.962
1.148
1.185 (1.129)
N 2O
0.774
NO
H2
105.1
H 2O
1.150
0.820
2.106
1.831
2.804
2.586
2.632
2.804
2.731
2.679
2.631
Au4
2.648
2.784
2.751
2.593
2.753
Au4(H2)
Au4(NO)
[3.09]
[10.96]
0.796
1.126
1.922
2.740
2.674
2.723
2.746
Au4+
2.094
2.836
2.836
2.711
2.731
2.656
2.617
2.733
2.733
2.817
Au4+(H2)
Au4+(NO)
[11.73]
[12.81]
1 H2NON2OH2OAu4Au4+Au2z(NO) Au2z(H2)(z=0,+1), kcal mol-1

HAuN O .
1.2.2 Au4+ NO
Au4+ H2 + 2NO N2O + H2O
2 3, 1
2, Au4+(H2)2NO Au4+(2NO)H2
2 1 1 2.0
2 NO
-3-
SJFCD
NO O H O-H H-H TS12
34.53 kcal mol -1TS1-2 NO O-H
H-H 2 2 N7-O8 1.384 1.493 O8-H10 4.820

1.334 TS2-3TS2-3 N 2O H2O 58.46 kcal mol-1
2 2 NO N Au H2O NO 4 4
TS4-5 5 TS4-5 H-H H O
46.71 kcal mol-1 5 TS5-6 6 TS5-6 N-O O-H
19.07 kcal mol-1 6 H2O
1.793
1.136
0.799
2.084
1.909
2.820
2.823 2.701 2.737
1.133
5
9
6
8
1.240 71.384
2.180 4.820
3
2.849
2.635
10 1.657
2
1
4
2.693 2.756
1.145
1.216
1.172
1.178
1.647
2.727
2.789
2.863
2.722
2.656
1
TS1-2
1.119
1.166
1.124
6 5
2.198 7 9
8
3
1.334
2.646 2.723 10
1.703
1
4
2
2.727 2.684
0.964
2.686
2.718
1.451
2.179
2.672
TS4-5
2.684
4
1.502 0.861
2.683
2.676
2.674
3
2.833
2.120
2.145
0.746
2.851
2.755
2.694
TS2-3
2.702
1.153
2.149 3.016
1.330
1.145
1.928
2.827 2.182
2.710
2.665
2.682
2.816
2.713
2.717
2.667
1.165
1.123
1.693
2.151
2.810
2.685
2.684
TS5-6
3.063
2.662
2 Au4+ HAuN O .
-4-
SJFCD
TS4-5
20
Au4++2NO+H2
TS1-2
11.96
0.00
-1
Relative Energy (kcal mol )
23.29
-20
1
-22.57
TS2-3
-17.61
4
-23.42
-40
2
-45.22
TS5-6
-40.62
-60
5
-59.69
Au4++N2O+H2O
-80
-75.72
6
-96.07
-100
3
-96.15
3 Au4+ Au4+NO H2
(kcal mol-1).
,H2 H2
1 34.53 kcal mol -1 11.96 kcal mol-1
-1
Relative Energy (kcal mol )
2 46.71 kcal mol -1

1.2.2 Au4 NO
40
TS10-11
28.65
20
TS7-8
25.80
7
Au4+2NO+H2 -0.34
0
0.00
-20
TS8-9
10
-13.48
-31.94
8
-39.30
-40
-60
TS11-12
-38.22
11
-55.82
9
-87.48
-80
Au4+N2O+H2O
-75.72
12
-91.16
-100
4 Au4 Au4NO H2
(kcal mol-1)
-5-
SJFCD
1.986
1.572
1.221
1.475
2.833
0.817
1.233
1.125
1.846
2.009
2.790
1.644
2.758
2.681
2.755
2.845
2.792
2.822
2.798
2.660
2.727
2.728
2.766
TS7-8
2.653
2.759
0.743
1.324
1.065
1.192
1.121
1.158
1.459
0.969
2.165
2.163
3.825
2.000
1.135
2.322
1.164
2.081 1.953
2.840
2.649
2.835
2.674
2.752
2.733
2.749
2.704
2.742 2.596
TS8-9
2.790
2.651
10
1.571
0.832
1.394
1.875
1.557
2.121
2.814
2.725
2.660
2.184
2.205
2.749
TS10-11
2.628
2.813
2.781
2.629
2.611
1.609
2.816
2.774
2.617
TS11-12
11
1.102
1.172
1.124
2.995
2.182
0.972
2.621
2.836
2.763
2.600
12
5 Au4 HAuN O
PES , 7 (Au4(H2)2NO) 10 (Au4(2NO)H2)

( 4), 3 4 5 3 , 7 H2
H Au4H-H , H Au , Au , N ,
NO O H2 H , TS7-8 26.14 kcal mol -1,
H NO Au4H H-H Au-H , O-H ,
8 8 TS8-9 9 TS8-9 , N-O , H-OH
7.36 kcal mol -1
-6-
SJFCD
4 TS10-11 TS11-12 5
IRC
4 : H2
H2 PES 26.34 42.13
kcal mol -1 25.80 28.65 kcal mol -1
(Au4 Au4+) NO H2
H2 H2
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