Zhongtian Du 1 , Junxia Liu 1,2 , Tianliang Lu 1,2 , Yangyang Ma 1,2 & Jie Xu 1*
1 State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National
Laboratory for Clean Energy, Dalian 116023, China
2 University of Chinese Academy of Sciences, Beijing 100049, China
Received July 30, 2014; accepted, 2014
*Corresponding author (email: xujie@dicp.ac.cn)
1

Figure S1 Schematic depiction of the ATR-IR apparatus. 1. Gas inlet; 2. Mettler-Toledo diamond probe; 3.
thermocouple; 4. pressure gauge; 5. relief valve; 6. gas vent; 7.
stir bars;
8. heater; 9. magnetic stirrer; 10. reaction mixture including catalysts, substrate, and solvent.
1704 cm -1
1147 cm -1
Figure S2 Operando ATR-IR spectra when benzyl alcohol was oxidized. Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol NaNO
2
, 0.25 mmol VOSO
4
, 5 mL acetonitrile, 25 μL H
2
O, 0.3 MPa O
2
, 80 o
C.
2

60
40
20
100
80
0
NaNO
2
NaNO
3
HNO
Nitrogen Source
3 isoamyl nitrite
Figure S3 Effect of nitrogen sources. Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol VOSO
4
, 0.25 mmol [N], 5 mL acetonitrile, 25 μL H
2
O, 80 o C, 0.5 MPa O
2
, 2 h.
Entry: HNO
3
(65% – 68%), without addition of 25 μL H
2
O. The data for NaNO
3
was based on ATR-IR results.
NaNO
3
NaNO
2
0.25
0.20
0.15
0.10
0.05
0.00
0 60 120
Time / min
180 240
Figure S4 Formation of benzaldehyde using NaNO
2
and NaNO
3
respectively monitored by ATR-IR.
Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol NaNO
2
(or NaNO
3
),
0.25 mmol VOSO
4
, 5 mL acetonitrile, 25 μL H
2
O, 80 o
C, 0.3 MPa O
2
.
3

1671 cm -1
1306 cm -1
922 cm -1
Charge O
2
Figure S5 ATR-IR spectra of vapor phase after subtraction of the acetonitrile background .
0.4
1308
0.3
0.2
0.1
1674
924
0.0
1800 1600 1400
Wavenumber / cm
-1
1200 1000
Figure S6 ConcIRT spectrum after oxygen was charged (about ConcIRT spectrum see
Ref. [1]).
4

Conversion of benzyl alcohol
Selectivity for benzaldehyde
60
40
20
100
80
0 bubble O
2
0.1 0.3
0.5
Partial Pressure of Oxygen / MPa
Figure S7 The effect of the partial pressure of oxygen. Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol NaNO
2
, 0.25 mmol VOSO
4
, 5 mL acetonitrile, 25 μL H
2
O, 80 o
C, 2 h. Entry: 0.1 MPa, reaction time: 3 h.
0.3 MPa
0.5 MPa
0.25
0.20
0.15
0.10
0.05
0.00
0 60 120
Time / min
180 240
Figure S8 Catalytic oxidation of benzyl alcohol under different oxygen pressure monitored by ATR-IR. Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol NaNO
2
,
5

0.25 mmol VOSO
4
, 5 mL acetonitrile, 25 μL H
2
O, 80 o C.
100
80
60
40
20
0
VOSO
4
Ce ( SO
4
)
2
FeSO
4
Sulphate
CuSO
4
SnSO
4
Figure S9 Catalytic oxidation of benzyl alcohol using different sulphates. Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol NaNO
2
, 0.25 mmol sulphates, 5 mL acetonitrile, 25 μL H
2
O, 80 o C, 0.5 MPa O
2
, 2 h.
3
2 a
400 b
551
1
0
300 400 500 600
Wavelength / nm
700 800 900
Figure S10 Detection of vanadium (V) by UV-Vis spectroscopy (900 – 260 nm). (a) Blank ground of PAR (pyridyl azo resorcinol) and INT (iodo-nitro-tetrazolium chloride); (b) PAR and INT chelated with the mixture derived from VOSO
4
/NaNO
2
.
6

(a)
(b)
0 -200 -400 -600
51
V Chemical Shift / ppm
-800 0 -200 -400 -600
51
V Chemical Shift / ppm
-800
Figure S11 Detection of vanadium (V) by
51
V NMR. (a) VOSO
4
aqueous solution; (b)
VOSO
4
/NaNO
2
was pretreated under 80 o
C, O
2
, 2 h, and then dissolved in DMSO.
1146 1114 t
1300 1200
Wavenumber / cm
-1
1100
Figure S12 Transition of IR bands from 1114 to 1146 cm

1
(stack lines).
1000
7

1704 cm -1 1146 cm -1
Figure S13 ATR-IR spectra for catalytic oxidation of benzyl alcohol in the top viewport.
1704
1147 t
160 min
140 min
120 min
100 min
80 min
60 min
40 min
20 min
0 min
1800 1600 1400 1200
Wavenumber / cm
-1
1000
Figure S14 ATR-IR spectra for catalytic oxidation of benzyl alcohol (stack lines).
8

0.30
0.25
0.20
1st 2 nd
Peak at 1704 cm
-1
Peak at 1727 cm
-1
0.15
0.10
0.05
N
2
O
2
0.00
0 60 120 180
Time / min
240 300 360
Figure S15 Oxidation of benzyl alcohol in two steps. Reaction conditions: 5 mmol benzyl alcohol, 0.25 mmol VOSO
4
, 0.25 mmol NaNO
2
, 5 mL acetonitrile, 25 μL H
2
O, 80 o
C. 1 st
step: 0.1 MPa N
2
; 2 nd step: 0.3 MPa O
2
, and 0.1 MPa N
2
.
Figure S16 Photos of VOSO
4
in water. (1) VOSO
4
/NaNO
2
, 80 o
C, O
2
, water, 2 h; (2)
VOSO
4
dissolved in water at room temperature.
9

A B
Figure S17 Photos of VOSO
4
/NaNO
2
reaction mixture. (A) 0.25 mmol VOSO
4
, 0.25 mmol NaNO
2
, 25 μL water, 5 mL acetonitrile, 0.5 MPa O
2
, 80 o
C, 10 h; ( B ) 0.5 mmol benzyl alcohol was added to solution A , then the mixture was stirred under 0.1 MPa N
2
, 80 o
C, 5 h.
Scheme S1 VOSO
4
/NaNO
2 catalyzed oxidation of 1-phenylethanol and 1-hexanol.
1 He C, Zhang GH, Ke J, Zhang H, Miller JT, Kropf AJ, Lei AW. Labile Cu(I) catalyst/spectator Cu(II) species in copper-catalyzed C–C coupling reaction: operando IR, in situ XANES/EXAFS evidence and kinetic investigations. J Am Chem Soc , 2013, 135:
488-493
10