Ternary platinum–cobalt–indium nanoalloy on ceria as a highly efficient catalyst for the oxidative dehydrogenation of propane using CO2

Abstract

The oxidative dehydrogenation of propane using CO2 (CO2-ODP) is a promising technique for high-yield propylene production and CO2 utilization. Developing a highly efficient catalyst for CO2-ODP is of great interest and benefit to the chemical industry and for carbon recycling. However, the efficiency of the existing catalysts is limited. Here, we report a Pt-Co-In ternary nanoalloy on CeO2 having a (Pt1−xCox)2In3 pseudo-binary alloy structure, which exhibits a considerably high catalytic activity, C3H6 selectivity, stability, and CO2 utilization efficiency at 550 °C. Alloying Pt with In and Co significantly improves the C3H6 selectivity and CO2 reduction ability, respectively. The Co species provide a high density of states near the Fermi level, which lowers the energy barrier of CO2 reduction.The catalyst stability is drastically enhanced by combining the strong CO2 activation ability of the alloy and the CeO2 support capable of oxygen release, which facilitate Mars-van Krevelen-type coke combustion.

Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook

“…The ternary Pt–Co–In/CeO 2 catalyst was developed recently for this process and showed promising results at 550 °C: the conversion of propane was about 50% at the 95% propylene selectivity due to the nanoalloys of Pt with Co and In and efficient reagent activation by metallic Pt–Co–In and ceria species. 162…”

High-entropy intermetallics on ceria as efficient catalysts for the oxidative dehydrogenation of propane using CO2

“…This is because the oxygen vacancy of CeO 2 must be refilled for the continuous combustion. In this regard, we previously confirmed by H 2 -TPR and CO 2 -TPO that the oxygen atoms derived from CO 2 refilled the oxygen vacancy of CeO 2 14 . Then, C 3 H 8 conversion was fully recovered when HIE/CeO 2 was regenerated under flowing CO 2 and the subsequent H 2 reduction, demonstrating that coke accumulated on the catalyst can be completely removed.…”

“…80%), the CO 2 utilization efficiency (excess CO 2 is necessary) and catalyst stability were low. Transition metal-based catalysts like Pd, Fe 3 Ni, and Pt–Co–In 5 , 13 , 14 have been receiving more attention in CO 2 -ODP, owing to their multifunctional properties for simultaneous activation of propane and CO 2 15 – 17 . C–H activation of propane and CO 2 reduction can be mediated by noble metals (Pt and Pd) 18 , 19 and the late 3d transition metals (Co, Ni, and Cu) 20 , 21 , respectively; thus, an appropriate combination of these metals allows for the construction of a dual functional catalyst for propane and CO 2 conversion.…”

“…C–H activation of propane and CO 2 reduction can be mediated by noble metals (Pt and Pd) 18 , 19 and the late 3d transition metals (Co, Ni, and Cu) 20 , 21 , respectively; thus, an appropriate combination of these metals allows for the construction of a dual functional catalyst for propane and CO 2 conversion. Using CeO 2 or Ce-based oxides as a support of the metallic phase is also a promising way for CO 2 -ODP owing to various promotional effects such as Mars-van Kreveren-type CO 2 activation 13 , 22 , 23 or coke combustion 14 , 24 , and strong metal-support interaction to tune the character of the active phase 25 , 26 . We recently reported that the Pt–Co–In/CeO 2 catalyst exhibited remarkably high catalytic activity and CO 2 utilization efficiency 14 .…”

“…Using CeO 2 or Ce-based oxides as a support of the metallic phase is also a promising way for CO 2 -ODP owing to various promotional effects such as Mars-van Kreveren-type CO 2 activation 13 , 22 , 23 or coke combustion 14 , 24 , and strong metal-support interaction to tune the character of the active phase 25 , 26 . We recently reported that the Pt–Co–In/CeO 2 catalyst exhibited remarkably high catalytic activity and CO 2 utilization efficiency 14 . However, irreversible catalyst deactivation still occurred, which was likely caused by the accumulation of incombustible coke and nanoparticle sintering.…”