Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts

John C Matsubu; Shuyi Zhang; Leo DeRita; Nebojsa S Marinkovic; Jingguang G Chen; George W Graham; Xiaoqing Pan; Phillip Christopher

doi:10.1038/nchem.2607

Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts

Nat Chem. 2017 Feb;9(2):120-127. doi: 10.1038/nchem.2607. Epub 2016 Sep 19.

Authors

John C Matsubu¹, Shuyi Zhang^{2

3}, Leo DeRita¹, Nebojsa S Marinkovic⁴, Jingguang G Chen^{4

5}, George W Graham^{2

3}, Xiaoqing Pan^{2

6}, Phillip Christopher^{1

7

8}

Affiliations

¹ Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521, USA.
² Department of Chemical Engineering and Materials Science, University of California, Irvine, Irvine, California 92697, USA.
³ Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA.
⁴ Department of Chemical Engineering, Columbia University, New York 10027, USA.
⁵ Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA.
⁶ Department of Physics and Astronomy, University of California, Irvine, Irvine, California 92697, USA.
⁷ Program in Materials Science, University of California, Riverside, Riverside, California 92521, USA.
⁸ UCR Center for Catalysis, University of California, Riverside, Riverside, California 92521, USA.

PMID: 28282057
DOI: 10.1038/nchem.2607

Abstract

The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal-support interactions can be exploited to optimize metal active-site properties are lacking. Here we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCO_x) on reducible oxide supports (TiO₂ and Nb₂O₅) that induce oxygen-vacancy formation in the support and cause HCO_x-functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO₂-reduction selectivity.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't