Proceedings of the 4th International Conference on Nanostructures (ICNS4) 12-14 March, 2012, Kish Island, I.R.

Iran

Development of LaCoxFe1-xO3 perovskite nano catalysts for reduction of NOx with NH3
A. Niaei, D. Salari*, P. Nakhostin Panahi, S. M. Mousavi, S. Arefi Oskoui Department of Applied Chemistry & Chem. Eng., Faculty of Chemistry, University of Tabriz, Tabriz, 5166016471, Iran *e-mail@ corresponding authors address: Prof of Applied Chemistry, Email: salari.dariush@gmail.com

Abstract: Some perovskite nano catalyst was studied for the Selective Catalytic Reduction of NOx with ammonia
(NH3-SCR) at low and high temperatures (100-400 C). Nano structured LaFeO3 and LaCoxFe1-xO3 perovskite type oxides with x=0, 0.1, 0.2 and 0.3 were prepared by the sol-gel auto-combustion method. Their structure and surface properties were investigated by X-ray diffraction (XRD), Fourier transmission infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). With this preparation method, a good inclusion of the substituting cobalt cation in B-site is reached. The catalytic activity of the catalysts in NOx reduction increased with an increase in cobalt substitution.

Keywords: NOx reduction; perovskite; selective catalytic reduction (SCR); LaCox Fe1-xO3 Introduction
The increasing usage of fossil fuels has led to appearance of various problems in human life. NOx, generally refers to a mixture of NO and NO2 produced by combustion engines and industrial processes, contribute to different atmospheric pollution phenomena, acid rains, photochemical smog, global warming and the depletion of the stratospheric ozone layer [1]. With the increasing concerns about environmental protection, the control of NOx emissions has become important and efficient methods are required in order to meet more stringent regulations [2]. One possible approach for reduction of NOx to N2 is selective catalytic reduction (SCR) with ammonia. The use of NH3-SCR has been investigated for several years and is today a well established technique for De-NOx in stationary sources [3]. The best suggested reactions for this process are as followings [4]: 4NH3 + 4NO + O2 4N2 + 6H2O 2NH3 + NO + NO2 2N2 + 3H2O A review on the literature shows that the main catalytic systems applied in NO removal are the following two systems: M-Supports (M: Transitional and noble metal Supports: Zeolites, Active Carbon, Alumina), metal oxides and composite mixed oxides. Composite mixed oxides, mostly with perovskite-type structure (ABO3 or A2BO4), can be seen as interesting alternatives as they are low-cost materials and stable even at above 1000C. Thus, from the standpoint of the catalyst lifetime (structural stability) and the catalyst manufacturing cost, which are two important criterions for industrial catalyst, perovskite-type mixed oxides could be a potential candidate for NOx removal. Perovskite are mixed oxides with a specific cubic structure and can be described by the general formula ABO3. Perovskites have previously been investigated for SCR [5]. The objectives of this work are to synthesize LaCoxFe1-xO3 (x=0, 0.1, 0.2 and 0.3) perovskites in the form of nanoparticles by the sol-gel combustion method and used for selective catalytic reduction (SCR) of NOx with ammonia.

Experimental Perovskite catalysts preparation

Analytical grade Fe(NO3)39H2O, La(NO3)36H2O, Co(NO3)2.6H2 O and C6H8O 7H2O were used for catalysts preparation. The desired amount of Fe(NO3)39H2O, La(NO3)36H2O and Co(NO3)2.6H2O were dissolved in citric acid solution to obtain substituted LaCoxFe1-xO3 (x=0, 0.1, 0.2, 0.3). The solutions were evaporated with vigorously stirring for 2h then the slurry burned and turned into a brown powder. The obtained brown powder was calcined at 600 C for 1h.

Perovskite catalysts characterization

The phases of the synthesized catalysts were characterized by X-ray diffraction (XRD) using a Siemens D500, X-ray powder diffractometer equipped with a position-sensitive detector, allowing all angles between 4 and 80 to be read simultaneously, at a scan rate of 2 /min. Monochromatic CuK was used as the radiation source. The mean crystal sizes were estimated using the Scherrer equation [6]. The FT-IR transmission spectra in the region of 400-4000cm-1 were recorded for all the samples using FT-IR Nexus 670 by KBr pellet technique. The scanning electron microscope (SEM) images were performed by means of a Joel JEM-100 CXII microscope.

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Measurement of catalytic activity

The catalysts activities in NOx reduction were studied at atmospheric pressure in a fixed bed flow reactor (a glass tube 10 mm internal diameter and 3 cm length). A mixture of Ar, O2, NO and NH3 (as reducing agent) was mixed in a mixing chamber and introduced into the reactor. The concentration of O2, NO and NH3 was 5%, 500 ppm and 500ppm, respectively. In each run, 0.2 g of catalyst was used for catalytic tests. The gas hourly space velocity (GHSV) was 6000 h-1, and the reaction temperature ranged from 100-400C. The concentration of N2 (as selective product) in the outlet of the reactor was measured by a gas chromatograph with a thermal conductivity detector (TCD).

The XRD patterns of LaFeO3 and LaCoxFe1-xO3 samples are showed in Figure 2. Fig. 2(a) shows XRD pattern of pure perovskite-type oxide of LaFeO3 with an orthorhombic structure. The diffraction data is in good agreement with LaFeO3 (JCPDS 37-1493) [8]. There is no distinguishable difference between the XRD patterns of LaFeO3 and LaCoxFe1-xO3, this shows perovskite structure in LaCoxFe1-xO3 samples. Also there is no clear difference between the XRD patterns of LaCoxFe1-xO3 samples, indicating complete doping of cobalt. But with increasing cobalt content, observed an almost linear shift toward higher 2. These results are in agreement with FTIR result, indicating complete doping of cobalt cations in to perovskite structure. Furthermore, using the Scherrer equation, the average particle sizes of the perovskites were determined to be 23-33 nm.

Results and Discussion Catalysts Characterization

Figure 1 shows the FT-IR spectra of LaCoxFe1-xO3 perovskites. In FT-IR spectra, bands around 1150-1600 cm-1 in all samples are ascribed to nitrogen containing organic compounds (NO2 functional group) [6]. The strong bands around 550-580 cm-1 correspond to the OFe-O vibration. A shift to higher wave number is observed with incorporation of cobalt, where in case of x=0.3 the highest shift value was observed. The broad weak bond between 3418 and 3440 cm-1 is due to rapid absorption of moisture by KBr [7]. These means that no segregate phase were formed during incorporation of cobalt.

Fig 2. XRD patterns of LaCoxFe1-xO3 nanocatalysts. SEM images of LaFeO3 are shown in fig. 3. These images show a uniform grain size distribution, a fine powder size and homogenous nano structure.

Fig 3. SEM images of (a) LaFeO3 ( 500x ), (b) LaFeO3 (10000x)

Catalysts Activity
In order to determine a suitable range of temperatures for the NOx reduction to occur in the prepared perovskites, experiments under temperature programmed conditions have been carried out. The prepared perovskite catalysts were tested for selective catalytic reduction (SCR) of NOx with ammonia in temperatures of 100, 200, 300 and 400C. The results are shown in Fig. 4. It observes that the NOx conversion is increased with increasing of

Fig 1. FT-IR spectra of the LaCoxFe1-xO3 nanocatalyst calcined at 800 C in air for 3h.

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temperature and an acceptable conversion is reached in 400C. With compared the activity of LaFeO3 and LaCoxFe1-x O3 catalysts, we observed that with introduce of cobalt, the active increased. The NOx reduction capacity of the LaFeO3 perovskite is the lowest. Also the activity of LaCoxFe1-x O3 was increased with an increase in cobalt insertion. The sample LaCo0.3Fe0.7O3 removes NOx at temperatures from 200 C (43.67 %), and reaches a maximum NOx removal level of 69.37 % which is maintained at 300 C. Substitution modifies the surface structure of the catalyst by greatly increasing the oxygen valances in the surface regions, which results in higher catalytic activity. It has been reported that the catalytic activity of perovskite type ABxB1-xO3 is related with the metal-oxygen bond and the free energy of reduction of the cation placed at B and B sites [9,10].

[6] U. Zaryalova, B. Nigrovski, K. Pollok, F. Langenhorst, B. Mller, P. Scholz, B. Ondruschka, Appl. Catal. 83 (2008) 221-228. [7] C.C. Chang, H.S. Weng, Ind. Eng. Chem. Res. 31(1992) 1615. [8] M. Sivakumar, A. Gedanken, W. Zhong, Y.H. Jiang, Y.W. Du, I. Brukental, D. Bhattacharya, Y. Yeshurun, I. Nawik, J Mater. Chem. 14 (2004) 764. [9] G. Pecchi, P. Reyes, R. Zamora, L.E. Cads, J.L.G. Fierro, J Solid state Chem. 181 (2008) 905. [10] M.A. Pena, J.L.G. Fierro, Chem. Rev. 101 (2001) 1981.

Fig 4. Catalytic activity of LaFeO3 and LaCoxFe1-xO3 for reduction NOx

Conclusions
Nanostructured LaFeO3 and LaC0xFe1-xO3 (x=0, 0.1, 0.2 and 0.3) perovskites were successfully synthesized using the sol-gel combustion method. We observed that with introduce of cobalt, the active increased. Also the activity of LaCoxFe1-xO3 was increased with an increase in cobalt insertion.

References
Journal article [1] J.C. Calvert, Pure Appl. Chem. 69 (1997) 1. [2] A. Tomita, Fuel Process. Technol. 71 (2001) 53. [3] Hanna Sjovall, Louise Olsson, Erik Fridell, Richard J. Blint. Applied Catalysis B: Environmental 64 (2006) 180. [4] V.I. Parvulescu, P. Grange, B. Delmon, Catalytic removal of NO, Catalysis Today 46 (1998) 233316. [5] Junjiang Zhu, Arne Thomas. Applied Catalysis B: Environmental 92 (2009) 225-233.

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