AUTHOR=Thum Lukas , Riedel Wiebke , Milojevic Natasa , Guan Chengyue , Trunschke Annette , Dinse Klaus-Peter , Risse Thomas , Schomäcker Reinhard , Schlögl Robert TITLE=Transition-Metal-Doping of CaO as Catalyst for the OCM Reaction, a Reality Check JOURNAL=Frontiers in Chemistry VOLUME=10 YEAR=2022 URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2022.768426 DOI=10.3389/fchem.2022.768426 ISSN=2296-2646 ABSTRACT=

In this study, first-row transition metal-doped calcium oxide materials (Mn, Ni, Cr, Co., and Zn) were synthesized, characterized, and tested for the OCM reaction. Doped carbonate precursors were prepared by a co-precipitation method. The synthesis parameters were optimized to yield materials with a pure calcite phase, which was verified by XRD. EPR measurements on the doped CaO materials indicate a successful substitution of Ca2+ with transition metal ions in the CaO lattice. The materials were tested for their performance in the OCM reaction, where a beneficial effect towards selectivity and activity effect could be observed for Mn, Ni, and Zn-doped samples, where the selectivity of Co- and Cr-doped CaO was strongly reduced. The optimum doping concentration could be identified in the range of 0.04-0.10 atom%, showing the strongest decrease in the apparent activation energy, as well as the maximum increase in selectivity.