Abstract
NiO and metal-promoted NiO catalysts (M-NiO, with a M/(M+Ni) atomic ratio of 0.08, with M = Nb, Sn, or La) have been prepared, tested in the oxidative dehydrogenation (ODH) of ethane, and characterized by means of XRD, TPR, HRTEM, Raman, XPS, and in situ XAS (using H/He, air or CH/He mixtures). The selectivity to ethylene during the ODH of ethane decreases according to the following trend: Nb-NiO ≈ Sn-NiO > La-NiO > NiO, whereas the catalyst reducibility (determined by both TPR and XAS using H/He mixtures) shows the opposite trend. However, different reducibility and catalytic behavior in the absence of oxygen (ethane/He mixtures) have been observed, especially when comparing Nb- and Sn-promoted NiO samples. These differences can be ascribed mainly to a different phase distribution of the promoter. The results presented here are discussed in terms of the nature of active and selective sites for ODH of ethane in selective and unselective catalysts, but also the role of promoters and the importance of their phase distribution.
The authors would like to acknowledge the DGICYT in Spain CTQ2012-37925-C03-2, CTQ2015-68951-C3-1-R, and CTQ2015-68951-C3-3-R. Authors thank European Synchrotron Radiation Facility, ESRF (Project CH-4512; BM25-SpLine Beamlime). Authors from ITQ also thank Project SEV-2016-0683 for financial support. D.D. thanks MINECO and Severo Ochoa Excellence Program for his fellowship (SVP-2014-068669). B.S. also thanks UV-INV-AE16-484416. Finally, the authors thank the Electron Microscopy Service of Universitat Politècnica de València for their support.