Abstract
“Single - atom” catalysts (SACs) have been the focus of intense research, due to debates about their reactivity and challenges toward determining and designing “single - atom” (SA) sites. To address the challenge, in this work, we designed Pt SACs supported on Gd-doped ceria (Pt/CGO), which showed improved activity for CO oxidation compared to its counterpart, Pt/ceria. The enhanced activity of Pt/CGO was associated with a new Pt SA site which appeared only in the Pt/CGO catalyst under CO pretreatment at elevated temperatures. Combined X-ray and optical spectroscopies revealed that, at this site, Pt was found to be d-electron rich and bridged with Gd-induced defects via an oxygen vacancy. As explained by density functional theory calculations, this site opened a new path via a dicarbonyl intermediate for CO oxidation with a greatly reduced energy barrier. These results provide guidance for rationally improving the catalytic properties of SA sites for oxidation reactions.
| Original language | English |
|---|---|
| Pages (from-to) | 12582-12588 |
| Number of pages | 7 |
| Journal | Chemical Science |
| Volume | 14 |
| Issue number | 44 |
| DOIs | |
| State | Published - Oct 17 2023 |
Funding
Y. L., H. S., S.D.S., Z. W. and D. J. acknowledge support of this work by the U.S. Department of Energy (U. S. DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. A. I. F., H. W. and R. G. N. acknowledge support of the U. S. DOE, Office of Science, Office of Basic Energy Sciences grant no. DE-SC0022199. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (U. S. DOE, Office of Science, Office of Basic Energy Sciences, Grant No. DE-SC0012335). This research used the QAS (7-BM) beamline of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-05CH11231. We thank Drs S. Ehrlich, L. Ma and N. Marinkovic for expert help during beamline experiments. We thank Prof. I. Lubomirsky for useful discussions of the properties of doped ceria.