Propane dehydrogenation over extra-framework In(i) in chabazite zeolites

Indium on silica, alumina and zeolite chabazite (CHA), with a range of In/Al ratios and Si/Al ratios, have been investigated to understand the effect of the support on indium speciation and its corresponding influence on propane dehydrogenation (PDH). It is found that In2O3 is formed on the external surface of the zeolite crystal after the addition of In(NO3)3 to H-CHA by incipient wetness impregnation and calcination. Upon reduction in H2 gas (550 °C), indium displaces the proton in Brønsted acid sites (BASs), forming extra-framework In+ species (In-CHA). A stoichiometric ratio of 1.5 of formed H2O to consumed H2 during H2 pulsed reduction experiments confirms the indium oxidation state of +1. The reduced indium is different from the indium species observed on samples of 10In/SiO2, 10In/Al2O3 (i.e., 10 wt% indium) and bulk In2O3, in which In2O3 was reduced to In(0), as determined from the X-ray diffraction patterns of the product, H2 temperature-programmed reduction (H2-TPR) profiles, pulse reactor investigations and in situ transmission FTIR spectroscopy. The BASs in H-CHA facilitate the formation and stabilization of In+ cations in extra-framework positions, and prevent the deep reduction of In2O3 to In(0). In+ cations in the CHA zeolite can be oxidized with O2 to form indium oxide species and can be reduced again with H2 quantitatively. At comparable conversion, In-CHA shows better stability and C3H6 selectivity (∼85%) than In2O3, 10In/SiO2 and 10In/Al2O3, consistent with a low C3H8 dehydrogenation activation energy (94.3 kJ mol-1) and high C3H8 cracking activation energy (206 kJ mol-1) in the In-CHA catalyst. A high Si/Al ratio in CHA seems beneficial for PDH by decreasing the fraction of CHA cages containing multiple In+ cations. Other small-pore zeolite-stabilized metal cation sites could form highly stable and selective catalysts for this and facilitate other alkane dehydrogenation reactions.