Supplementary Material for Journal of Porous Materials
Supporting Information
Highly ordered crystalline mesoporous metal oxides for hydrogen
peroxide decomposition
Mingshi Jin  Jung-Nam Park*  Jeong Kuk Shon  Zhenghua Li  Eunok Lee 
Ji Man Kim*
Department of Chemistry, BK21 School of Chemical Materials Science and
Department of Energy Science, Sungkyunkwan University, Suwon, 440-746, Republic
of Korea
*Corresponding authors. E-mail address: pjungnam@gmail.com (Jung-Nam Park);
jimankim@skku.edu (Ji Man Kim)
1. Preparation of meso-MOx by nano-replication method
The typical syntheses of mesoporous KIT-6 [1], CeO2, Co3O4, Cr2O3, Mn2O3 [2],
NiO, RuO2, SnO2 [3] and TiO2 are as follows.
1.1 Synthesis of Ia3d mesoporous silica KIT-6 and surface modified HP-KIT-6
In a typical synthesis, mesoporous silica template, KIT-6, was synthesized
following methods reported elsewhere [1].
A triblock copolymer (Pluronic P123,
EO20PO70EO20, Aldirch) and tetraethylorthosilicate (TEOS, Aldrich) were utilized as
the structure-directing agent and framework source, respectively. The template was
removed by extraction in an ethanol-HCl mixture (addition of 1 g of product in the
1
mixture of 20 ml ethanol and 2 ml concentrated HCl) for 1 h, followed by calcination
at 550 °C for 3 h. For modication of KIT-6 surface, after calcination, the silica surface
of KIT-6 was modified with methyl groups by refluxing a mixture containing 0.6 g
hexamethyldisilazane (HMDS, 99%, Fluka), 150 mL of n-hexane and 3.0 g of
calcined KIT-6. The material thus obtained is denoted as surface modified HP-KIT-6
(hydrophobic KIT-6).
1.2 Synthesis of meso-Co3O4, Cr2O3, Mn2O3, NiO and SnO2
The KIT-6 material was used as a template for the synthesis of meso-MOx replica
[2].
For
synthesis
of
meso-Mn2O3,
Manganese
(III)
nitratehexahydrate
(Mn(NO3)2·6H2O, Aldrich) was used as meso-Mn2O3 precursor. Typically, 5.0 g of
the calcined KIT-6 template was heated at 100 oC for 1 h. The pre-heated silica
template was poured into a polypropylene bottle containing 4.63 g of
Mn(NO3)2·6H2O (m.p. 37 oC) that was melted to liquid phase at 80 oC. The bottle
containing the mixture was closed and shaken vigorously to mix the Mn(NO3)2·6H2O
and KIT-6 template. Subsequently, the bottle was put in an oven at 80 oC overnight
for the spontaneous infiltration of manganese precursor within the mesopores of silica
template. The composite materials then were heated to 450 oC under ambient
atmosphere for 3 h. The silica template was removed by treating the composite
material with 2 M NaOH solution three times. Finally, the meso-Mn2O3 material thus
obtained was washed with distilled water and acetone several times and dried at 80 oC.
Elemental analysis indicated that the amount of residual silica template was below
than 0.1 wt%. For the synthesis of Co3O4, Cr2O3, NiO, SnO2, and TiO2 the precursors
(Aldrich); Co(NO3)2·6H2O (99%), Cr(NO3)3·9H2O (99%), Ni(NO3)2·4H2O (98%),
RuCl3·3H2O (99%), SnCl2·2H2O (99%), Ti(OCH(CH3)2)4 (99%) were used
respectively. The synthesis of meso-CeO2, Co3O4, Cr2O3, Mn2O3 NiO, SnO2, and
TiO2 is identical to that of meso-Mn2O3.
1.3 Synthesis of meso-RuO2 using surface modifed KIT-6
2
HP-KIT-6 (hydrophobic KIT-6) was used to synthesize the meso-RuO2. The
solution (containing 1.97 g RuCl3 (99%, Aldrich), 1.5 g EtOH and 1.5 g distilled
water) was impregnated into 5.0 g of the modified KIT-6 template by an incipient
wetness method. After drying at 80 oC for 24 h, the composite was heated to 300 oC
under nitrogen flow for 24 h. Subsequently, the silica template was completely
removed by treating the composite material with 3.0 M NaOH solution three times at
0 oC. Finally, the meso-RuO2 material was washed with distilled water and acetone
several times and dried in a vacuum oven at room temperature for 12 h.
2. Preparation of bulk-MOx by conventional precipitation method
2.1 Synthesis of bulk-CeO2, Co3O4, Cr2O3, Mn2O3, NiO and SnO2
The typical synthesis of bulk-CeO2 [4], Co3O4 [5], Cr2O3 [6], Mn2O3 [7], NiO [8]
and SnO2 [9] are as follows. For the synthesis of CeO2, 30 mL of 1.0 M of NH4OH
was added drop by drop in to 100 mL of 0.1 M aqueous solution of Ce(NO3)3·6H2O,
leading to the formation of a precipitation. During the precipitation, the formed
suspension was strongly mixed. A precipitate was then collected by vacuum filtration,
washed with distilled water several times, dried at room temperature for 48 h, and
finally calcined at 500 oC under air environment for 3 h. The Co3O4, Cr2O3, Mn2O3,
NiO, RuO2 and SnO2 were also synthesized by the precipitation method with identical
procedure using corresponding metal precursor with meso-MOx.
2.2 Synthesis of bulk-RuO2
For the preparation of RuO2 [10], 60 mL of 1.0 M of NH4OH was added drop by
drop in 200 mL of 0.02 M aqueous solution of RuCl3·3H2O (99%), leading to the
formation of a precipitation up to pH 5.1. During the precipitation, the formed
suspension was strongly mixed. And then, 30% H2O2 solution was added drop by
drop in the mixture and stirred for 4 h. A black precipitate was then collected by
vacuum filtration, washed with distilled water. Wet precipitates were redispersed into
40 ml of distilled water using an ultrasound bath, then autoclaved at 160 oC for 2 h.
3
The precipitates was then collected by vacuum filtration, washed with distilled water
several times, dried at room temperature for 48 h, and finally calcined at 500 oC under
air environment for 3 h.
References
[1] J.K. Shon, S.S. Kong, J.M. Kim, C.H. Ko, M .Jin, Y.Y. Lee, S.H. Hwang, J.A.
Yoon, J.N. Kim, Chem.Commun. 650 (2009)
[2] J.-N. Park, J. Shon, M. Jin, S. Kong, K. Moon, G. Park, J.-H. Boo, J. Kim, Reac.
Kinet. Mecha. Catal. 103,87 (2011)
[3] J.K. Shon, S.S. Kong, Y.S. Kim, J.-H. Lee, W.K. Park, S.C. Park, J.M. Kim,
Microp. Mesop. Mater. 120, 441 (2009)
[4] M.J. Godinho, R.F. Goncalves, L.P.S. Santos, J.A. Varela, E. Longo, E.R. Leite,
Mater. Lett. 61,1904 (2007)
[5] C.-B. Wang, C.-C. Lee, J.-L. Bi, J.-Y. Siang, J.-Y. Liu, C.-T. Yeh, Catal. Today
146,76 (2009)
[6] Z. Pei, Y. Zhang, Mater. Lett. 62,504 (2008)
[7] S. Ordόṅez, J.R. Paredes, F.V. Díez, Appl. Catal. A: Gen 341,174 (2008)
[8] X. Deng, Z. Chen, Mater. Lett. 58, 276 (2004)
[9] L. Xi, D. Qian, X. Tang, C. Chen, Mater. Chem. Phys. 108,232 (2008)
[10] S. Music, S. Popovic, M. Maljkovic, A. Saric, Mater. Lett. 58,1431 (2004)
4
Table S1. The used amounts of each precursor for synthesis of meso-MOx catalysts
Sample
KIT-6
meso-CeO2
meso-Co3O4,
meso-Cr2O3
meso-Mn2O3
meso-NiO
meso-RuO2
meso-SnO2
meso-TiO2
Precursor type
Ce(NO3)3∙6H2O
Co(NO3)2∙6H2O
Cr(NO3)3·9H2O
Mn(NO3)2∙6H2O
Ni(NO3)2∙6H2O
RuCl3∙3H2O
SnCl2∙6H2O
Ti(OCH(CH3)2)4
Amount (g)
5
3.19
6.16
2.37
4.50
4.86
1.73
5.09
6.72
5
Table S2. The related standard reduction potentials of metal ion, metal oxide and
metal hydroxide species of studied catalysts
Metal ion species
Metal oxide and metal hydroxide species
Catalyst
Reaction
E0 (V)a
E0 (V)a
CeO2
Ce4+ + e ⇔ Ce3+
1.72
Ce(OH)3+ + H+ + e ⇔ Ce3+ + H2O
1.715
Co3O4
Co3+ + e ⇔ Co2+
1.92
Co(OH)3 + e ⇔ Co(OH)2 + OH-
0.17
Cr(V) + e ⇔ Cr(IV)
1.34
Cr2O72- + 14H+ + 6e ⇔ 2Cr3+ + 7H2O
1.232
Mn2O3 + 6H+ + e ⇔ 2Mn2+ + 3H2O
1.485
MnO4- + 4H+ + 3e ⇔ MnO2 + 2H2O
1.679
Mn(OH)3 + e ⇔ Mn(OH)2 + OH-
0.15
Ni(OH)2 + 2e ⇔ Ni + 2OH-
-0.72
RuO2 + 4H+ +2e ⇔ Ru2+ 2H2O
1.120
SnO2 + 4H+ + 2e- ⇔ Sn2+ + 2H2O
-0.094
TiO2 + 4H+ + 2e ⇔ Ti2+ + 2H2O
-0.502
Cr2O3
Cr + e ⇔ Cr
3+
Mn2O3
NiO
2+
Mn3+ + 3e ⇔ Mn2+
-0.407
1.541
Ni2+ + 2e ⇔ Ni
-0.257
Ru3+ + e ⇔ Ru2+
0.248
Ru + 2e ⇔ Ru
0.455
Sn2+ + 2e ⇔ Sn
-0.137
Sn4+ + 2e ⇔ Sn2+
0.151
RuO2
2+
SnO2
Ti3+ + e ⇔ Ti2+
-0.9
TiO2
Ti + 3e ⇔ Ti
3+
a
Reaction
-1.37
: the values of standard reduction potentials
6
Fig. S1. N2 adsorption-desorption isotherms of bulk-MOx. a) CeO2, b) Co3O4, c)
Cr2O3, d) Mn2O3, e) NiO, f) RuO2, g) SnO2, and h) TiO2
7
Fig. S2. O2-TPO patterns of (a) meso-MOx, and (b) bulk-MOx. a) CeO2, b) Co3O4, c)
Cr2O3, d) Mn2O3, e) NiO, f) RuO2, g) SnO2 and h) TiO2
8
Fig. S3. H2-TPR patterns of (a) meso-MOx, and (b) bulk-MOx. a) CeO2, b) Co3O4, c)
Cr2O3, d) Mn2O3, e) NiO, f) RuO2, g) SnO2 and h) TiO2
9