skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on June 15, 2019

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

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., In 3+, Ga 3+, Zn 2+, Mn 2+, and Ti 4+/SiO 2). 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/SiO 2 catalysts. Finally, these fundamental studies and the developed activity–descriptor relationship open up new opportunities for rational design of hydrogenation catalysts.
Authors:
 [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
Publication Date:
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357; NNCI-1542205; DMR-1121262
Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 152; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrogenation; metal ion; DFT; activity descriptor; silica
OSTI Identifier:
1460193