Supporting Information
Size-dependent chemical reactivity of porous graphene for
purification of exhaust gases
Chen Si Gang Zhou*
Department of Chemistry, University of Science and Technology Beijing,
Beijing 100083; Department of Physics, Tsinghua University, Beijing
100084, People's Republic of China
*
Corresponding author:gzhou@phys.tsinghua.edu.cn
Starting from the initial states, and following the coordination rule in heterogeneous
reaction, that is, “higher valency adsorbate occupies higher coordination site”, we first
confirmed the primary information of final states for the three reactions, further
calculated and compared the total energies of possible final states, finally obtained the
most stable final states as mentioned in the paper. The detailed processes of the
identification of final states are shown below.
N-attack of NO2 on the vacancy
Figure S1 Possible final states of N-attack of NO2 on the vacancy: (a) only one O atom
of NO2 bonds with the weak bond, (b) two O atoms of NO2 bond with the weak bond
together.
Table S1 The relative energy of (a) with respect to (b), which is set to zero.
Configuration
a
b
Relative energy (eV)
0.46
0
O-attack of NO2 on the vacancy
Figure S2 Possible final states of O-attack of NO2 on the vacancy. The dissociated O of
released NO group on (a) the bridge of the N-C2 bond, (b) the top of the C2, and (c) the
bridge of the C2-C bond.
Table S2 The relative energies of (a) and (b) with respect to (c), which is set to zero.
Configuration
a
b
c
Relative energy(eV)
1.80
0.42
0
NO on the vacancy
Figure S3 Possible final states of NO on the vacancy: following the coordination rule of
heterogeneous reaction, the N occupies the vacancy, with the dissociated O at some
possible sites, containing the top of the N atom (T1), the top of nearest C atom (T2), the
top of the next nearest C atom (T3), the center of the nearest hexagonal ring (C1), the
center of the next nearest carbon hexagon (C2), the bridge of the N-C2 bond (B1) and the
bridge of the C2’-C bond (B2).
TableS3 The relative energies of N-doped graphene with O adsorption at different sites,
with respect to the T2 site. The energy of B1 is absent because the O atom moves to T2
after structural relaxation. The total energy of T2 is set to zero.
Site
T1
T2
T3
C1
C2
B1
B2
Relative energy (eV)
1.84
0
0.18 0.36 1.95
-0.57