TY - JOUR
T1 - Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica
AU - Liu, Cong
AU - Camacho-Bunquin, Jeffrey
AU - Ferrandon, Magali
AU - Savara, Aditya
AU - Sohn, Hyuntae
AU - Yang, Dali
AU - Kaphan, David M.
AU - Langeslay, Ryan R.
AU - Ignacio-de Leon, Patricia A.
AU - Liu, Shengsi
AU - Das, Ujjal
AU - Yang, Bing
AU - Hock, Adam S.
AU - Stair, Peter C.
AU - Curtiss, Larry A.
AU - Delferro, Massimiliano
N1 - Funding Information:
This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences , Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC02-06CH11357 ( Argonne National Laboratory ). DFT calculations were performed using the computational resources at the Argonne National Laboratory (ANL), Center for Nanoscale Materials (CNM) and resources provided by the Laboratory Computing Resource Center (LCRC) at ANL. Use of the Advanced Photon Source is supported by the U.S. Department of Energy, Office of Science, and Office of the Basic Energy Sciences, under Contract DE-AC-02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. Microkinetic modeling was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC05-00OR22725 (ORNL). The XPS work made use of the facilities of the NU ANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource ( NSF NNCI-1542205 ); the MRSEC Program (NSF DMR-1121262 ) at the Materials Research Center ; the International Institute for Nanotechnology ( IIN ); the Keck Foundation ; and the State of Illinois, through the IIN.
PY - 2018/9/15
Y1 - 2018/9/15
N2 - 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., In3+, Ga3+, Zn2+, Mn2+, and Ti4+/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.
AB - 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., In3+, Ga3+, Zn2+, Mn2+, and Ti4+/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.
KW - Activity descriptor
KW - DFT
KW - Hydrogenation
KW - Metal ion
KW - Silica
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U2 - 10.1016/j.poly.2018.06.006
DO - 10.1016/j.poly.2018.06.006
M3 - Article
AN - SCOPUS:85049305956
VL - 152
SP - 73
EP - 83
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -