Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2015
Astam K. Patra,
[a, b]
Sudipta K. Kundu,
[a]
Dukjoon Kim,*
[b] and Asim Bhaumik*
[a] cctc_201402871_sm_miscellaneous_information.pdf

Table of Content
Section 1 TEM Images of NO-1C and NO-2C samples
Section 2 FESEM images of NO-1C and NO-2C samples
Section 3 N
2
sorption of NO-1C and NO-2C samples
Section 4 Reaction kinetics of the reduction of benzaldehyde
Section 5 Recycling efficiency of the hexagonal-shaped NiO (NO-1C) catalyst
Section 6 TON and TOF
Section 7 Synthesis procedure of NiO nanoparticle.
Section 8 N
2
sorpation and wide angle XRD of Nano NiO and Bulk NiO
Section 9
1
H and
13
C NMR data of different alcohol product.
1

Section 1: TEM Images of NO-1C and NO-2C samples
Figure S1.
TEM images of a) self-assembled structure of NO–1C nanocrystal, b) single hexagonal shape particle with (111) lattice fringes and FFT is shown in the inset of this
Figure. c) self-assembled structure of NO–2C nanocrystals, d) single hexagonal shape particle with (111) crystal lattice fringes.
2

Section 2: FESEM images of NO-1C and NO-2C samples
Figure S2.
FESEM images of a) self-assembled structure of NO–1C nanocrystal, b) selfassembled structure of NO–2C nanocrystals.
3

Section 3: N
2
sorption of NO-1C and NO-2C samples
Figure S3 . (a) N
2
adsorption (●)–desorption (○) isotherms at 77 K of (a) NO–1C and its pore size distribution is sown in inset (b) NO–2C and its pore size distribution is sown in inset.
Pore size distribution is calculated using the Non Local Density Functional Theory (NLDFT)
Model.
4

Section 4: Kinatics study
Figure S4 . Reaction kinetics of the reduction of benzaldehyde.
5

Section 5: Catalyst recycling test
Figure S5 : Recycling efficiency of the hexagonal-shaped NiO (NO-1C) catalyst.
6

Section 6: TON and TOF
Table S1 . Reduction reaction of benzaldehyde in different condition
Catalyst H-Source
Temp
(
0
C)
Time
(h)
Conversion TON a
TOF b
Ref
Ru(η
6
Cymene)(Cl)(L)
[{RuCl
-p-
2
[{Cp*IrCl
(pcymene)}]
[{Cp*RhCl
2
2
}
2
}
2
2
]
]
2-propanol-
KOH
H
2
O-
HCOONa
H
2
O-
HCOONa
H
2
O-
HCOONa
80
65
65
65
1
25
25
25
89.0
32
35
70
267
-
-
-
267
2
3
20
1
2
2
2
[{Cp*IrCl
2
}
2
]-
Ts(en),IPA
[{Cp*IrCl
2
}
2
]-
CF
3
Ts(en)
NO-1C
(Hexagonal shape)
NO-2C
(Hexagonal shape)
2-propanol
H
2
O-
HCOONa
2-propanol-
KOH
2-propanol-
KOH
65
80
25
25
1
1
12
12
2.6
98
83.2
82.7
-
-
3.1
3.1
26
132000
0.26
0.26
2
2
This work
This work
Nano NiO
2-propanol-
KOH
25 12 71.0 2.6 0.21
This work
Bulk NiO
2-propanol-
KOH
25 12 56.3 2.1 0.17
This work a
TON (turnover number) = number of moles of substrate converted/number of moles of active site of the catalyst. b
TOF (turnover frequency) = TON per hour
7

Section 7: Synthesis procedure of NiO nanoparticle
Synthesis procedure of NiO nanoparticle: Nickel oxide nanoparticle was prepared by a hydrothermal crystallization method. The sample was prepared following a well−known procedure. At first, Ni(NO
3
)
2
·6H
2
O (0.1 mol) and CO(NH
2
)
2
(0.4 mol) was dissolved into 60 mL of deionized water respectively with vigorous stirring. Then the two solutions were mixed in a beaker and stirred at room temperature until a homogeneous solution obtained.
The mixture solution was transferred into a round bottom flask heated at 115°C for 1.5 hrs in an oil bath. After the reaction was completed, precipitated powder was collect by filtration and washed several times with water. The powder was dried in an oven at 90°C and calcined in air at 400°C for 1 h to form NiO nanoparticle.
8

Section 8: N
2
sorpation and wide angle XRD of Nano NiO and Bulk NiO
Figure S6 . (a) N
2
adsorption (●)–desorption (○) isotherms at 77 K of (a) nano NiO and its pore size distribution is sown in inset (b) Bulk NiO and its pore size distribution is sown in inset. Pore size distribution is calculated using the Non Local Density Functional Theory
(NLDFT) Model.
Figure S7 . Wide angle XRD pattern of (a) nano NiO and (b) Bulk NiO.
9

Section 9:
1
H and
13
C NMR data of different alcohol product.
Benzyl alcohol (Table 2 entry 1) ,
1
H NMR (500 MHz, CDCl
3
7.28-7.38 (m, 5H);
13
C NMR (500 MHz, CDCl
3
) δ 2.27 (b, 1H), 4.66 (s, 2H),
) δ 65.45, 127.12, 127.77, 128.69, 140.98.
2-bromobenzyl alcohol (Table 2 entry 2) ,
1
H NMR (400 MHz, CDCl
3
) 4.76 (s, 2H), 7.15-
7.19 (m, 1H), 7.32-7.36 (m, 1H), 7.48-7.56 (m, 2H);
13
C NMR (400 MHz, CDCl
3
) δ 65.26,
122.76, 127.82, 129.10, 129.29, 132.78, 139.92.
4- bromobenzyl alcohol (Table 2 entry 3) ,
1
H NMR (500 MHz, CDCl
3
) δ 2.46 (b, 1H), 4.59
13
(s, 2H), 7.18-7.20 (d, 2H, J = 10 Hz), 7.44-7.46 (d, 2H, J = 10 Hz); C NMR (500 MHz,
CDCl
3
) δ 64.54, 121.52, 128.68, 131.70, 139.83.
4-chlorobenzyl alcohol (Table 2 entry 4) ,
1
H NMR (500 MHz, CDCl
3
) δ 2.07 (b, 1H), 4.59
(s, 2H), 7.23-7.31 (m, 4H);
13
C NMR (500 MHz, CDCl
3
) δ 65.38, 128.67, 129.56, 133.03,
139.57.
4-fluorobenzyl alcohol (Table 2 entry 5),
1
H NMR (500 MHz, CDCl
3
) δ 2.75 (b, 1H), 4.58
(s, 2H), 6.99-7.03 (m, 2H), 7.27-7.29 (m, 2H);
13
C NMR (500 MHz, CDCl
3
) δ 64.39, 115.29,
128.77, 136.60, 161.37.
4-methylbenzyl alcohol (Table 2 entry 6),
1
H NMR (300 MHz, CDCl
(s, 3H), 4.63 (s, 2H), 7.16-7.18 (d, 2H), 7.24-7.27 (d, 2H);
3
) δ 1.97 (b, 1H), 2.36
13
C NMR (300 MHz, CDCl
3
) δ
21.25, 65.30, 127.22, 129.33, 137.47, 138.04.
4-nitrobenzyl alcohol (Table 2 entry 7),
1
H NMR (500 MHz, CDCl
(s, 2H), 7.53-7.55 (d, 2H, J = 10 Hz), 8.21-8.23 (d, 2H, J = 10 Hz);
3
) δ 1.67 (b, 1H), 4.84
13
C NMR (500 MHz,
CDCl
3
) δ 64.19, 123.90, 127.15, 148.24.
2-nitrobenzyl alcohol (Table 2 entry 8),
1
H NMR (500 MHz, CDCl
3
) δ 2.28 (b, 1H), 4.95
(s, 2H), 7.43-7.46 (m, 1H), 7.63-7.66 (m, 1H), 7.71-7.72 (m, 1H), 8.06-8.08 (m, 1H);
13
C
NMR (500 MHz, CDCl
3
) δ 62.67, 125.15, 128.63, 130.11,134.25, 136.93, 147.83.
( pyridin-2-yl)methanol (Table 2 entry 9),
1
H NMR (500 MHz, DMSO-d
6
) δ 2.38 (b, 1H),
4.54 (s, 2H), 7.44-7.46 (m, 1H), 7.65-7.68 (m, 1H), 7.75-7.81 (m, 1H), 8.42-8.46 (m, 1H);
13
C NMR (500MHz, DMSO-d
6
) δ 64.23, 120.18, 121.91, 136.59, 148.44, 161.91.
1-(4-iodophenyl)ethanol (Table 2 entry 10),
1
H NMR (500 MHz, CDCl
3
) δ 1.47-1.48 (d,
3H, J = 5Hz), 2.58 (b, 1H), 4.85-4.86 (q, 1H), 7.12-7.14 (m, 2H), 7.66-7.70 (m, 2H);
13
C
NMR (500 MHz, CDCl
3
) δ 25.33, 69.97, 92.83, 127.55, 137.74, 145.56.
1-(4-bromophenyl)ethanol (Table 2 entry 11),
1
H NMR (500 MHz, CDCl
3
) δ 1.39-1.40 (d,
3H, J = 5Hz), 2.51 (b, 1H), 4.79-4.80 (q, 1H), 7.16-7.19 (m, 2H), 7.38-7.40 (m, 2H);
13
C
NMR (500 MHz, CDCl
3
) δ 25.36, 69.94, 127.29, 129.99,131.70,135.98.
1-(4-fluorophenyl)ethanol (Table entry 12),
1
H NMR (500 MHz, CDCl
3
) δ 1.37-1.38 (d,
3H, J = 5 Hz), 2.54 (b, 1H), 4.64-4.67 (q, 1H), 6.90-6.92 (m, 2H), 7.91-7.93 (m, 2H);
13
C
NMR (500 MHz, CDCl
3
) δ 22.02, 70.25, 115.70, 127.20, 130.78, 162.18.
10

1
H NMR of benzyl alcohol
13
C NMR of benzyl alcohol
11

1
H NMR of 2-bromobenzyl alcohol
13
C NMR of 2-bromobenzyl alcohol
12

1
H NMR of 4-bromobenzyl alcohol
13
C NMR of 4-bromobenzyl alcohol
13

1
H NMR of 4-chlorobenzyl alcohol
13
C NMR of 4-chlorobenzyl alcohol
14

1
H NMR of 4-fluorobenzyl alcohol
13
C NMR of 4-fluorobenzyl alcohol
15

1
H NMR of 4-methylbenzyl alcohol
13
C NMR of 4-methylbenzyl alcohol
16

1
H NMR of 4-nitrobenzyl alcohol
13
C NMR of 4-nitrobenzyl alcohol
17

1
H NMR of 2-nitrobenzyl alcohol
13
C NMR of 2-nitrobenzyl alcohol
18

1
H NMR of ( pyridin-2-yl)methanol
13
C NMR of ( pyridin-2-yl)methanol
19

1
H NMR of 1-(4-iodophenyl)ethanol
13
C NMR of 1-(4-iodophenyl)ethanol
20

1
H NMR of 1-(4-bromophenyl)ethanol
13
C NMR of 1-(4-bromophenyl)ethanol
21

1
H NMR of 1-(4-fluorophenyl)ethanol
13
C NMR of 1-(4-fluorophenyl)ethanol
22

Reference
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[2] X. Wu, J. Liu, X. Li, A. Zanotti-Gerosa, F. Hancock, D. Vinci, J. Ruan, J. Xiao, Angew.
Chem . 2006, 118, 6870 –6874; Angew. Chem. Int. Ed.
2006 , 45, 6718 –6722.
23