A simple additive-free approach for the synthesis of uniform manganese monoxide nanorods with large specific surface area
© Zheng et al.; licensee Springer. 2013
Received: 17 January 2013
Accepted: 13 March 2013
Published: 11 April 2013
A simple additive-free approach is developed to synthesize uniform manganese monoxide (MnO) one-dimensional nanorods, in which only manganese acetate and ethanol were used as reactants. The as-synthesized MnO nanorods were characterized in detail by X-ray diffraction, scanning and transmission electron microscopy (TEM) including high-resolution TEM and selected-area electron diffraction, Fourier transform infrared spectrum, and nitrogen adsorption isotherm measurements. The results indicate that the as-synthesized MnO nanorods present a mesoporous characteristic with large specific surface area (153 m2 g−1), indicating promising applications in catalysis, energy storage, and biomedical image. On the basis of experimental results, the formation mechanism of MnO one-dimensional nanorods in the absence of polymer additives was also discussed.
KeywordsManganese monoxide Nanorods Additive-free synthesis Formation mechanism
During the past decade, manganese oxides have attracted considerable research interest due to their distinctive physical and chemical properties and potential applications in catalysis, ion exchange, molecular adsorption, biosensor, and energy storage [1–12]. Particularly, nanometer-sized manganese oxides are of great significance in that their large specific surface areas and small sizes may bring some novel electrical, magnetic, and catalytic properties different from that of bulky materials. A wide variety of manganese oxides (e.g., MnO2, Mn2O3, and Mn3O4) have been synthesized through various methods [13–24]. Among them, manganese monoxide (MnO) is a model system for theoretical study of the electronic and magnetic properties of rock salt oxides , and its nanoclusters interestingly exhibit ferromagnetic characteristics . On the other hand, MnO is very interesting for its lower charge potential (1.0 V vs. Li/Li+) compared to other transition metal oxides . It has been reported that a relatively high voltage and energy density can be obtained when it was coupled with a certain cathode material to construct a full lithium ion cell .
In terms of the synthesis methods of MnO, several approaches have been developed to prepare nanostructured MnO with different morphologies [28–42], such as hydrothermal reactions and subsequent annealing , thermal decomposition of Mn-containing organometallic compounds [29–32], thermal decomposition of MnCO3 precursor [33, 34], vapor-phase deposition , etc. More recently, Lin et al. reported a simple one-pot synthesis of monodispersed MnO nanoparticles (NPs) using bulk MnO as the starting material and oleic acid as solvent . Sun et al. reported a microwave-polyol process to synthesize disk-like Mn complex precursor that was topotactically converted into porous C-modified MnO disks by post-heating treatment . However, these methods are often associated with the use of high-toxicity, environmentally harmful, and high-cost organic additives. Moreover, the by-products may have a detrimental effect on the size, shape, and phase purity of the MnO NPs obtained. It still remains a major challenge to prepare high-quality monophase MnO NPs due to the uncontrollable phase transformation of multivalent manganese oxides (MnO2, Mn2O3, and Mn3O4).
In the present work, we report a simple, cost-effective, and additive-free method for the synthesis of uniform MnO nanorods with large specific surface area, in which cheap manganese acetate and ethanol were used as starting materials. The microstructures of the as-synthesized products were investigated using scanning electron microscopy (SEM) and transmission electron microscope (TEM). The as-synthesized MnO nanorods present a mesoporous characteristic and large specific surface area. More importantly, we have avoided the use of expensive polymer or surfactant additives during the synthesis process. The possible formation mechanism for MnO nanorods in the absence of polymer additives was also discussed.
Preparation of MnO nanorods
In a typical synthesis, 1.0 g of manganese acetate was put into 30 mL of anhydrous ethanol distilled freshly to form a homogeneous solution under stirring. The solution was transferred to a 40-mL Teflon-lined stainless steel autoclave. These manipulations were operated in a glove box under N2 atmosphere. The autoclave was heated at 200°C for 24 h in an electric oven. After cooling to room temperature, the final products were washed with deionized water and ethanol several times and subsequently dried at 80°C for 6 h in vacuum.
Instruments and characterization
The phase purity of the obtained samples was examined by X-ray diffraction (XRD) using an MSAL-XD2 X-ray diffractometer with CuKα radiation (λ = 0.15406 nm) operating at 40 kV and 20 mA. Morphologies of the samples were characterized by field emission scanning electron microscopy (JSM6700F). The morphology and structure of the MnO nanorods were further investigated by TEM and high-resolution transmission electron microscopy (HRTEM; JEM-2010, 200 kV) with energy-dispersive X-ray spectroscopy (EDS; INCA X200). X-ray photoelectron spectroscopy (XPS) was carried out by means of a Shimadzu AXIS UTLTRADLD spectrometer (Shimadzu, Kyoto, Japan). Nitrogen adsorption-desorption measurements were performed using a Micromeritics Tristar 3000 gas adsorption analyzer (Micromeritics Instrument Co., Norcross, GA, USA). Fourier transform infrared (FTIR) spectrum was measured by an Equinox 55 (Bruker, Ettlingen, Germany) spectrometer ranging from 400 to 4,000 cm−1.
Results and discussion
In summary, uniform mesocrystalline MnO nanorods were prepared successfully by using manganese acetate and ethanol as starting materials. The as-synthesized MnO nanorods exhibited uniform morphology, large specific surface area, and narrow pore size distribution. The simple, cost-effective, and environmentally friendly synthesis can be scaled up to produce large quantities of porous MnO one-dimensional nanorods. Owing to their large specific surface area, the as-prepared MnO nanorods may have promising applications in energy storage, catalysis, and biomedical image. This method may also open a new avenue for the simple synthesis of porous functional materials with applications in the fields of energy and environment.
This work was financially supported by the National Natural Science Foundation of China (21201065 and 21031001), the Natural Science Foundation of Guangdong Province (s2012040007836), the Key Program of Science Technology Innovation Foundation of Higher Education Institutions of Guangdong Province (cxzd1014), and the Minister Funds of South China Agricultural University.
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