Highly Efficient Elimination of Carbon Monoxide with Binary Copper-Manganese Oxide Contained Ordered Nanoporous Silicas
© Lee et al. 2016
Received: 4 August 2015
Accepted: 14 December 2015
Published: 7 January 2016
Ordered nanoporous silicas containing various binary copper-manganese oxides were prepared as catalytic systems for effective carbon monoxide elimination. The carbon monoxide elimination efficiency was demonstrated as a function of the [Mn]/[Cu] ratio and reaction time. The prepared catalysts were characterized by Brunauer-Emmett-Teller (BET) method, small- and wide-angle X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HR-TEM) for structural analysis. Moreover, quantitative analysis of the binary metal oxides within the nanoporous silica was achieved by inductively coupled plasma (ICP). The binary metal oxide-loaded nanoporous silica showed high room temperature catalytic efficiency with over 98 % elimination of carbon monoxide at higher concentration ratio of [Mn]/[Cu].
Methods to effectively eliminate carbon monoxide have attracted much attention [1–5]. Recently, the related materials have been reported by different groups. It would be better to cite some examples [6–8]. Even though these supported noble metal-based catalysts have shown high activities for carbon monoxide elimination, their further application has been limited due to difficulties in reuse, sintering at high temperature, and high cost [9–12]. For this reason, the development of transition metal oxide catalysts as alternatives has gained much interest.
Transition metal oxides like CuOx, MnOx, and FeOx have so far been used for the elimination of carbon monoxide in bimetallic forms [13–15]. Recently, the related materials have been reported by different groups. It would be better to cite some examples [16, 17]. The binary Cu-Mn oxides have flexible metal valences (Cu1+/2+ and Mn3+/4+) which give rise to their specific properties and notable catalytic activities in carbon monoxide elimination [18, 19]. In particular, the incomplete Mn1.5Cu1.5O4 spinel structure of the binary Cu-Mn oxide catalyst was more active in the removal of carbon monoxide at room temperature than that of the same spinel structure with CuO [19–21]. In addition, its level of activity in removing carbon monoxide was reduced if the catalyst was calcined at a temperature above 500 °C, at which the crystallization of the spinel occurs.
Porous materials are typically used for separation, biological immobilization, catalysts, and supports, because of their high surface area and unique physical and chemical properties [22–27]. Porous materials such as zeolites have also been employed as supports for metal oxide nanoparticles for the removal of carbon monoxide [28, 29]. However, such materials limit the incorporation of nanoparticles into the micropores, as well as the diffusion of the reactant, due to irregular micropores. For these reasons, ordered porous structures with high surface area and mesopore size, such as MCM-41 and SBA-15, have been widely used as catalyst supports [26, 27]. Consequently, various metal oxide-loaded mesoporous silica catalysts, such as Fe/SBA-15, CuO/SBA-15, and CuO-CeO2/SBA-15, have been studied and observed to provide improved performance in carbon monoxide elimination [23, 30, 33]. However, as yet, there has been little study of binary CuMnOx-loaded mesoporous silica for the elimination of gaseous phase carbon monoxide.
Herein, we report on binary CuMnOx-loaded mesoporous silica catalysts, prepared using a co-precipitation method, and their catalytic performance for gaseous carbon monoxide elimination, achieved at ambient temperature with various types of [Mn]/[Cu] ratios. This co-precipitation method allowed for room temperature synthesis of amorphous binary CuMnOx with high catalytic activity for CO elimination at room temperature. The CO elimination results demonstrate that CuMnOx@MS-4 (with a [Mn]/[Cu] volume ratio of 4/1) can efficiently achieve >98 % elimination of CO gas within 420 min at room temperature.
Poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene) triblock copolymer (Pluronic P123, PEO20PPO70PEO20), hydrochloric acid, tetraethyl orthosilicate (TEOS), manganese nitrate hexahydrate, and copper nitrate trihydrate were used from Sigma-Aldrich. All chemicals were used as received without any further purification.
Synthesis of Ordered Mesoporous Silica (MS)
The ordered mesoporous silica support was synthesized following our previously reported method [23, 24]. Tri-block copolymer Pluronic P123 was dissolved in aqueous hydrochloric acid solution (1 < pH < 2) under vigorous stirring at 40 °C. A clear solution was obtained by incubating a complete dissolution of the surfactant. The tetraethyl orthosilicate (TEOS) was added into the solution at 40 °C as a silica source. The mixture was aged in a stainless steel bomb at 120 °C overnight. The precipitate was filtered, washed with excess water, air-dried at room temperature, and calcined at 550 °C.
Synthesis of Binary Metal Oxide-Loaded Ordered Mesoporous Silica Catalysts (CuMnOx@MS)
The CuMnOx@MS catalysts were prepared by co-precipitation method at ambient temperature with an aqueous solution of Cu(NO3)2 and Mn(NO3)2. An aqueous solution of Cu(NO3)2°3H2O (0.25 M) and Mn(NO3)2°6H2O (0.25 M) was pre-mixed and impregnated into the mesoporous silica. The CuMnOx@MS catalysts were synthesized as a function of various molar ratios of [Mn]/[Cu]. The compositions were in the range of [Mn]/[Cu] 1/1 (CuMnOx@MS-1), 2/1 (CuMnOx@MS-2), and 4/1 (CuMnOx@MS-4), respectively. Subsequently, an aqueous solution of Na2CO3 (2 M) was added to maintain the pH at 8. The composite was aged for 2 h and heated to 80 °C. The composite was recovered by filtration and washed several times with hot deionized water, air-dried at room temperature, and calcined at 400 °C for 2 h.
Small-angle X-ray scattering (SAXS) patterns were obtained on a Rigaku DMAX-2500 diffractometer using Cu-K α radiation (λ = 0.15418 nm) at 40 kV and 20 mA. The SAXS measurements were collected in the range 0.5°–4° of 2θ with a scanning speed of 2°min−1. Wide-angle X-ray diffraction (WAXD) patterns were recorded using a Rigaku DMAX-2500 Instrument with Cu-K α radiation. The samples were scanned in the range 20°–80° of 2θ with a scanning speed of 2°min−1.
Nitrogen adsorption-desorption isotherms were obtained with a Micromeritics TriStar II system. The Brunauer-Emmett-Teller (BET) method was utilized to calculate the surface areas. The pore size distribution curves were obtained from the desorption branch calculated by the Barrett-Joyner-Halenda (BJH) method. The morphological and structural details of the material were also studied by field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM). FE-SEM investigations were carried out with a JEOL JSM-6700 F instrument using 10 kV of accelerating voltage. Energy-dispersive X-ray spectroscopy (EDX) attached to the electron microscopy was used to qualitatively determine the elements present. HR-TEM was carried out on a JEOL JEM-4010 electron microscope operated at 400 kV. Cross-sectional slices of CuMnOx@MS, less than 60 nm in thickness, were prepared by using an ultramicrotome. To determine Cu, Mn, and Si ion contents in the various catalysts, the dried samples were weighed and digested with a mixed solution of phosphoric acid and ammonium metavanadate solution in sulfuric acid and hydrofluoric acid by heating. And then the Cu, Mn, and Si contents were analyzed, using inductively coupled plasma optical emission spectrometry (ICP-OES, Perkin Elmer instrument).
CO Elimination Test
The detection of CO elimination was performed by IR with a JASCO FTIR-460 spectrometer (resolution 4 cm−1, integration 20 times) and measured at room temperature. A sample was placed in an IR gas cell with KBr windows, and no treatment was applied before the measurement of elimination activity. 0.5 g of CuMnOx@MS catalyst was used in the IR gas cell. CO gas (50 mL) was added to the IR gas cell. The IR spectrum was obtained every 10 min at room temperature. The schematic of the CO elimination efficiency evaluation setup composed of a JASCO FTIR-460 spectrometer is shown in Additional file 1: Figure S1.
Results and Discussion
Physicochemical properties of the mesoporous silica and CuMnOx@MS samples synthesized with different Mn contents
Pore diameterb (nm)
Pore volumec (cm3 · g−1)
S BET d (m2 · g−1)
In this study, binary CuMnOx nanoparticle-loaded MS catalyst was successfully synthesized by co-precipitation and demonstrated for CO elimination at room temperature. Based on detailed characterizations, including SAXS, BET, and HR-TEM techniques, the binary CuMnOx nanoparticles were determined to be amorphous type with a diffraction peak similar to hopcalite. Moreover, the catalytic activity of the CuMnOx@MS catalysts was investigated for various [Mn]/[Cu] concentrations. With increasing [Mn] concentration, the catalytic activity was increased. Among these catalysts, CuMnOx@MS-4 showed the highest catalytic activity, of over 98 % CO elimination after 420 min at room temperature. The binary Cu-Mn metal oxide-loaded MS has good potential for practical applications to decrease CO in air pollution.
This work was supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Trade, Industry and Energy, Republic of Korea.
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