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

Journal Article · · Polyhedron
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With the increasing attention on single-site heterogeneous catalysts on account of their high specific activity, more effective catalyst design strategies are necessary. We demonstrate a first-principles-calculation-guided active-site design strategy for alkene hydrogenation using silica-supported single-atom single-site heterogeneous catalysts (SSHCs, i.e., M/SiO2). An activity-descriptor relationship for propylene hydrogenation was established using representative catalysts (i.e., Ga3+, Zn2+, Mn2+ and Ti4+/SiO2), correlating the computational activity descriptor (i.e., the reaction free energy of the metal hydride formation) with the experimental reaction rates. Microkinetic modeling confirmed the predicted reaction mechanisms and further explained the rationale of the activity-descriptor relationship. This relationship was then used to predict the trend of activities of a variety of isolated ions on silica, and an In3+/SiO2 catalyst was identified as the most promising candidate based on its predicted activity and synthetic feasibility. The monodispersed In3+/SiO2 catalyst was then synthesized, for the first time, and showed higher propylene hydrogenation activity than the other four single-atom SSHCs, as predicted. Detailed spectroscopic characterization (XAS, XPS, DRIFTS and DRUV-Vis) provided insights into coordination environments and oxidation states of the catalysts, as well as evidence for the hydride intermediate. The successful discovery of the In3+/SiO2 catalyst for propylene hydrogenation using the first-principles-calculations-guided design strategy opens up new opportunities for efficient development of single-atom SSHCs.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1462737
Journal Information:
Polyhedron, Vol. 152, Issue C; ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English

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