from first principles PP-I-1

PP-III-73Effect of B-Cation Substitution on the Activity of LaCrO 3 and LaNiO 3Perovskites for Autothermal Reforming of MethaneMota N. 1 , Matus E.V. 2 , Kuznetsov V.V. 2 , Ismagilov I.Z. 2 , Navarro R.M. 1 , Kerzhentsev M.A. 2 ,Ismagilov Z.R. 2,3 , Fierro J.L.G. 11 Instituto de Catálisis y Petroleoquímica, CSIC, Madrid, Spain2 Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia3 Institute of Coal Chemistry and Material Science SB RAS, Kemerovo, Russiaiismagil@catalysis.ruPerovskite-type oxides (ABO 3 ) are perspective catalysts for hydrocarbon conversion to COand H 2 [1]. Partial substitution of the A- or B-cations with other metals modifies the catalyticperformance due to the variation of redox properties and oxygen mobility [2]. The aim of thiswork is to study the effect of B-cation substitution on the activity of LaCrO 3 and LaNiO 3perovskites for autothermal reforming (ATR) of CH 4 . Substituted LaCr 1-x B x O 3 (B = Ni, Fe,Ru, Co, Mn, x = 0.15), prepared by Pechini method, and LaNi 1-x B x O 3 (B = Pt, Pd, Re, Sn,Mo, x = 0.01-0.05), prepared by citrate sol-gel method, were characterized by DTA-TG,XRD, N 2 adsorption (BET), TPR, XPS, HRTEM and tested in the ATR of CH 4 in a fixed-bedreactor with mass-spectrometric gas analysis. XRD showed that all the LaCr 1-x B x O 3 andLaNi 1-x B x O 3 samples have the LaCrO 3 and LaNiO 3 perovskite structures, respectively. InitialLaCrO 3 catalyst exhibits low ATR activity and gives mainly CO 2 at CH 4 conversion ~ 36 %(T = 850 o C). The substitution of Cr by Ni, Fe, Co or Mn has practically no effect on theproduct yield. On the contrary, using Ru the highest H 2 (~ 45 %) and CO (~ 65 %) yields atCH 4 conversion ~ 100% (T = 850 o C) were observed. Remarkably, substitution of Ni by В-cations in LaNiO 3 leads to an increase of S BET up to 2 times. We demonstrate that LaNi 1-xB x O 3 catalytic performance in the ATR of CH 4 can be regulated by the type and content ofB-cation. The particularities of ATR of CH 4 over LaCr 1-x B x O 3 and LaNi 1-x B x O 3 are revealedand correlated with the type of В-cation, structural and redox properties of these catalysts.The presented research has received funding from the European Union 7 th Framework Programme(FP7/2007-2013) under Grant Agreement #262840. The authors are thankful to Dr. V.A. Ushakov, Dr.T.Ya. Efimenko and Dr. G.S. Litvak from BIC SB RAS for their help with catalyst characterization.References:[1] N. Mota, M.C. Alvarez-Galván, R.M. Navarro, S.M. Al-Zahrani, A. Goguet, H. Daly, W. Zhang,A. Trunschke, R. Schlögl, J.L.G. Fierro, Appl. Catal. B Environ., 113-114 (2012) 271.[2] O.Yu. Podyacheva, Z.R. Ismagilov, A.N. Shmakov, M.G. Ivanov, A.N. Nadeev, S.V. Tsybulya,V.A. Rogov, Catal. Today 147 (2009) 270.228