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Title: Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica

Journal Article · · Polyhedron
 [1];  [1];  [1];  [2];  [1];  [1];  [1];  [1];  [3];  [4];  [5];  [6];  [7];  [8];  [5];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Dalian Inst. of Chemical Physics (China). Energy Research Resources Division
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Illinois Inst. of Technology, Chicago, IL (United States). Dept. of Chemistry
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
+ Show Author Affiliations

Single-site heterogeneous catalysts receive increasing attention due to their unique catalytic properties and well-defined active sites. In this paper, 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. Finally, these fundamental studies and the developed activity–descriptor relationship open up new opportunities for rational design of hydrogenation catalysts.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
National Science Foundation (NSF) (United States); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357; AC05-00OR22725
OSTI ID:
1460193
Journal Information:
Polyhedron, Journal Name: Polyhedron Vol. 152; ISSN 0277-5387
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
activity descriptor
hydrogenation
metal ion
silica