Supplementary data for:
Improve the activity and selectivity of Fenton
system in the oxidation of alcohols
Guoqiang Yang, Qiuxing Lin, Xingbang Hu*, Youting Wu*, Zhibing zhang
School of Chemistry and Chemical Engineering, and National Engineering Research
Center for Organic Pollution Control and Resource, Nanjing University, Nanjing
210093, P. R. China
Table S1. Effect of the amount of catalyst on the oxidation of benzyl alcohol a
Entry
FeSO4·7H2O NHPI
Conv. Sel.b
TOF
1
2
3
4
5
6
7
8
(mol%)
0.5
1
2
2.5
2.5
2.5
3.5
5
(%)
3.5
5.4
14.6
36.0
36.7
31.8
34.4
29.1
(/hour)
11.59
9.5
12.9
26.1
27.4
21.9
18.3
10.1
a
(mol%)
0.5
1
2
1.25
2.5
5
3.5
5
(%)
99.3(86:14)
99.2(89:11)
99.2(89:11)
98.2(92:8)
99.1(94:6)
95.9(90:10)
99.0(94:6)
97.0(90:10)
20 mmol of benzyl alcohol, 2.2 equiv. of H2O2 (30 wt% in water), catalyst (0.5
mol%-5 mol%), solvent free,25oC,30 min.H2O2 was added with a syringe pump by
0.2 ml/min speed. b Total selectivity to benzaldehyde and benzoic acid(ratio of
benzaldehyde/benzoic acid).
Table S2. Effect of the temperature on the oxidation of benzyl alcohol a
Entry
1
2
3
4
5
a
Temp.(oC)
10
25
40
55
70
Conv.(%)
8.6
36.7
50.2
55.0
46.5
Sel.b(%)
99.0(92: 8)
99.1 (94:6)
95.3 (91:9)
93.8(91:9)
93.5(92:8)
20 mmol of benzyl alcohol, 2.2 equiv. of H2O2 (30 wt% in water), solvent free, 30
min. H2O2 was added with a syringe pump by 0.2 ml/min speed. b Total selectivity to
benzaldehyde and benzoic acid (ratio of benzaldehyde/benzoic acid).
Figure S1. Benzyl alcohol conversion and selectivity with the reaction time. Reaction
conditions: 20 mmol of benzyl alcohol , solvent free,25oC,enough H2O2 was
continuously added with a syringe pump.&=by 0.3 ml/min speed;&=by 0.2
ml/min speed;&=by 0.15 ml/min speed;◆&◇=by 0.1 ml/min speed.
Figure S2. Effect of the iron-based catalysts. Reaction conditions: 20 mmol of benzyl
alcohol, 2.2 equiv. of H2O2 (30 wt% in water), Reaction time: 0.5 h. H2O2 was added
with a syringe pump by 0.2 ml/min speed.