Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica. (15th September 2018)

• Record Type: Journal Article
• Authors: Liu, Cong; Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Savara, Aditya; Sohn, Hyuntae; Yang, Dali; Kaphan, David M.; Langeslay, Ryan R.; Ignacio-de Leon, Patricia A.; Liu, Shengsi; Das, Ujjal; Yang, Bing; Hock, Adam S.; Stair, Peter C.; Curtiss, Larry A.; Delferro, Massimiliano
• Is Part Of: Polyhedron. Volume 152(2018)
• Page Start: 73
• Page End: 83
• Publication Date: 2018-09-15
• Subjects: Hydrogenation -- Metal ion -- DFT -- Activity descriptor -- Silica; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2018.06.006
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Experimental and computational studies of propylene hydrogenation using silica supported metal ion catalysts were carried out. An activity–descriptor relationship was developed showing a strong correlation between the experimental activity and the calculated free energy for the metal hydride formation, as a function of the metal. Abstract: Single-site heterogeneous catalysts receive increasing attention due to their unique catalytic properties and well-defined active sites. We report a combined computational and experimental study on a series of silica-supported metal ion hydrogenation catalysts (i.e., In 3+, Ga 3+, Zn 2+, Mn 2+, and Ti 4+ /SiO2 ). These catalysts were synthesized, characterized, and evaluated for gas-phase propylene hydrogenation. Computational studies were carried out on active-site structures and reaction mechanisms. An activity–descriptor relationship was established, which correlates a computational quantity (reaction free energy of the metal hydride formation) with the experimental reaction rate, as a function of the metal. Microkinetic modeling provided qualitative kinetic insights into the activity–descriptor relationship. This relationship was used to predict the trend of activities in a variety of M/SiO2 catalysts. These fundamental studies and the developed activity–descriptor relationship open up new opportunities for rational design of hydrogenation catalysts.