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Large-scale size-controlled synthesis of cryptomelane-type manganese oxide


OMS-2 in lateral and longitudinal directions
Qin Zhang, Xiaodi Cheng, Xionghan Feng,* Guohong Qiu, Wenfeng Tan and Fan Liu*
Received 14th December 2010, Accepted 14th February 2011
DOI: 10.1039/c0jm04370b

A facile method was developed to synthesize size-tunable OMS-2


nanomaterials using a series of saturated fatty carboxylic acids as
acid agents and regulators. The particle sizes, from 8.2 to 61.1 nm in
width and 35.6 to 1376.1 nm in length, can be precisely controlled by
decreasing alkyl chain lengths of carboxylic acids.
Porous manganese oxide octahedral molecular sieves (OMS) have
drawn significant interest due to their mixed-microporous structures,
large open tunnels, and high surface areas.1 Cryptomelane-type
manganese oxide is a group of the OMS family that shares duplex
chains on the same edge and the chains connect with a butted oxygen
to form a 2  2 tunnel structure known as octahedral molecular
sieve-2 (OMS-2).2 The unique physical and chemical properties of
OMS-2 have given this material a wide range of potential applications in gas sensing, catalysis, energy storage, separation (molecular
sieves), and battery materials.3 Hence, the preparation and potential
applications of bulk OMS-2 materials have been explored extensively.
During the past few years, a number of methods have been
developed to obtain OMS-2, such as solvent free, sol gel or ionic
liquid route, hydrothermal or aqueous route under refluxing conditions.4,5 Recently, increased attention has been paid to methods that
can control the particle size of OMS because the physicochemical
properties are closely related to the particle size.6 Although great
progress has been achieved in the synthesis of OMS-2, the synthesis
with controlled particle sizes still remains a challenge. It was reported
that the OMS-2 of controlled particle sizes was synthesized under
500600  C through an assisted solid-state method using different
cross-linking reagents (PVA, glycerol or glucose).7 Subsequently, the
particle size control of OMS-2 was accomplished through the
reduction of KMnO4 by changing the concentration of H2O2, or with
Mn2+ through adjusting the reaction conditions.8 A rapidly openvessel microwave-reflux route was recently developed to prepare size
tunable OMS-2 nanomaterials.9 However, even though the size of
Key Laboratory of Subtropical Agriculture Resource and Environment,
Ministry of Agriculture, College of Resources & Environment, Huazhong
Agricultural University, Wuhan, China. E-mail: fxh73@mail.hzau.edu.
cn; liufan@mail.hzau.edu.cn; Fax: +86 27 87280670; Tel: +86 27
87280271
Electronic supplementary information (ESI) available: Further details
in synthesis and analysis techniques, and HRTEM images and SAED
patterns of products, and the size distribution and the range, mean,
and standard deviation of particles size based on TEM images of
OMS-2 nanoparticles. See DOI: 10.1039/c0jm04370b

This journal is The Royal Society of Chemistry 2011

OMS-2 in lateral direction, such as the width, was effectively


controlled in above methods, the size in the longitudinal direction,
i.e. the length, is not well tuned at the same time. For example, the
widths of OMS-2 obtained by above methods were between 6 and
100 nm, but their length ranged from a few hundreds of nanometres
to several tens of micrometres. In addition, for these synthesis
methods, special instruments, complicated processes, long reaction
times, and/or relatively high temperatures are required. Therefore, it
is desirable to develop a simple, low-temperature, and low-cost
synthesis route for simultaneously controlling the particle sizes in
both width and length of OMS-2.
In this communication, we report a facile one-pot method to
control both width and length of OMS-2 by reflux of KMnO4 and
saturated fatty carboxylic acids at 100  C for 12 h. In a typical
synthesis, 50 mL aqueous mixture containing 0.3 mol of one of the
straight chain saturated fatty carboxylic acids with different alkyl
chain lengths (acetic acid (C2H4O2), propionic acid (C3H6O2), butyric
acid (C4H8O2), valeric acid (C5H10O2), and heptanoic acid
(C7H14O2)) is added to a 200 mL 0.4 mol KMnO4 solution, respectively. The XRD spectra of the products (see Fig. 1) show that all
products are OMS-2 (JCPDS no. 00-44-0141), confirming there is
little effect of acid type on the phase of final product. However,
differences are observed in the amplitudes and widths of the XRD
peaks, suggesting differences in particle sizes.

Fig. 1 XRD spectra of the products prepared with different carboxylic


acids: (a) C2H4O2, (b) C3H6O2, (c) C4H8O2, (d) C5H10O2 and (e)
C7H14O2.

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In order to further confirm the OMS-2 phase and determine the


morphology and size, the products were characterized by TEM,
HRTEM, and SAED. Fig. 2 shows the HRTEM and SAED of the
product prepared with heptanoic acid (C6H13COOH), and the
images of other carboxylic acids are shown in Fig. S1 and S2. Fig. 3
illustrates TEM images and average size of the OMS-2 as a function
of the alkyl chain length of the carboxylic acid. As shown in Fig. 2, 3
and S1, all crystallites are micro-morphologically one-dimension
nanowires. The HRTEM image in Fig. 2c shows interlayer spacings
of 0.484 and 0.240 nm, which correspond to the (200) and (211)
planes of monoclinic OMS-2. The d-spacings are also calculated
based on the polycrystalline SAED ring patterns in Fig. 2d and S2,
and the results are presented in Tables 1 and S1. All of the
d-spacings match the standard diffraction data for OMS-2 (JCPDS
no. 00-44-0141), and the result is consistent with the XRD. To
precisely evaluate the particle size of OMS-2, measurements were
made for 150 nanowires, such as those shown in Fig. 3, and the
average width and length were calculated. It is clear that as the alkyl
chain length of the carboxylic acids decreases from six carbons (hexyl)
to one carbon (methyl), the width of the resulting OMS-2 progressively increases from 8.2 to 61.1 nm while the length increases from
35.6 to 1376.1 nm. The length and width distributions of the OMS-2
nanoparticles are in Fig. S3. Obviously, with increasing alkyl chain
lengths of the applied carboxylic acids, both of the width and the
length decrease and the size distribution becomes narrower. In
addition, the range, mean and standard deviation of the particle
widths and lengths of OMS-2 for different carboxylic acids, shown in
Table S2, decrease with the increase of alkyl chain lengths, which is
consistent with the result in Fig. S3. All of these results suggest that
carboxylic acids with long alkyl chain lengths favour small and
uniform crystallites.
The products were analyzed by FTIR (Fig. 4) to determine the
sorption of carboxylic acids on the OMS-2 surface. In all FTIR
spectra, the characteristic adsorption bands for tunnel H2O bending

Fig. 2 HRTEM images (ac) and SAED pattern (d) of OMS-2 nanoparticles prepared with C7H14O2.

5224 | J. Mater. Chem., 2011, 21, 52235225

Fig. 3 TEM images and average size of the K-OMS-2 as a function of


the alkyl chain length of the carboxylic acids: (a) C2H4O2, (b) C3H6O2, (c)
C4H8O2, (d) C5H10O2 and (e) C7H14O2. The scale bars are 0.4 mm.

Table 1 Indexing of the ED pattern in Fig. 2d


Ring no.

Determined d/nm

Phase

Index h k l

Standard da/nm

1
2
3
4
5
6
7

0.689
0.484
0.307
0.239
0.214
0.182
0.154

C
C
C
C
C
C
C

110
200
310
211
301
411
521

0.692
0.489
0.309
0.240
0.215
0.183
0.153

OMS-2 (JCPDS file no. 00-44-0141).

band at 1633 cm 1 and for OMS-2 at 471, 523, 718, 1409 and 3446
cm 1 are observed.10 In the spectra of the products for C4H8O2,
C5H10O2 and C7H14O2, the bands near 3000 cm 1 of CH stretching
are observed, and the intensities of the bands increase with alkyl chain
length. The above FTIR results mean that the sorption densities of
saturated fatty acids increase with the alkyl chain length. The spectra
of C5H10O2 and C7H14O2 also display bands at 1714 cm 1 which are
due to C]O stretching of the COOH group. The FTIR data
indicate that part of carboxylic acids is adsorbed or segregated on the

Fig. 4 FTIR spectra of the products prepared with different carboxylic


acids: (a) C2H4O2, (b) C3H6O2, (c) C4H8O2, (d) C5H10O2 and (e)
C7H14O2.

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OMS-2 surface. It should be noted that due to the low solubility of


heptanoic acid in water, part of it maybe just segregate and adhere on
OMS-2 through hydrophobic effect and this may also be the case for
valeric acid.
The crystal growth process of OMS-2 has been documented in
the literature, and it usually proceeds following a dissolution
recrystallization mechanism through two steps: first, a disordered
or layered manganese oxide precursor forms. And in the second
step, the precursor dissolves and recrystallizes to form OMS-2
under certain conditions.4,8,11 The effect of carboxylic acids on the
crystal growth of OMS-2 may be the controlling mechanism.
Because newly formed manganese oxides have strong sorption
capacity,12 the external surfaces of the precursor and OMS-2
would sorb the carboxylic acids (Fig. 4) to form an organic film on
the surface. The sorbed carboxylic acids would hinder the dissolution of the layered manganese oxide precursor and subsequent
crystallization of OMS-2 due to its hydrophobicity and steric
effect. With increased alkyl chain length of the carboxylic acids,
the hydrophobicity increases and the solubility in water
decreases,13 thus the density of the sorbed carboxylic acid increases
in a controllable fashion as showed by FTIR results. Thus, by
controlling the alkyl chain length of the carboxylic acids, the
hindrance to the dissolutionrecrystallization process is effectively
controlled during the OMS-2 formation, and the crystal size of
OMS-2 becomes tunable.

Conclusions
In summary, a facile one-pot reflux method was developed to
synthesize OMS-2 nanowires with controlled particle sizes varying
from 8.2 to 61.1 nm in width and from 35.6 to 1376.1 nm in length
through the reaction of KMnO4 with different carboxylic acids. To
the best of authors knowledge, this is the first time for the OMS-2 to
be synthesized with controllable sizes in both longitudinal and lateral
dimensions of a broad range by tuning alkyl chain lengths of
carboxylic acids.

Acknowledgements
We would like to thank Dr C. Ni (University of Delaware, USA) for
his kind help on reviewing the final draft and improving the English.
We gratefully acknowledge the anonymous referees for their
constructive comments and helpful suggestions. This research was

This journal is The Royal Society of Chemistry 2011

sponsored by the National Natural Science Foundation of China


(40830527 and 40971142), and New Century Excellent Talents in
University (NCET-09-0399).

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