Abstract
Coupling catalyst characterization with reactivity measurements for studying mechanisms is state of the art in catalysis research. X-ray absorption (XAS) and other spectroscopies are limited in their ability to directly link the structure of catalytically active sites with the transformation of reactants that interact with the catalyst surface. We demonstrate that the substrate could play an additional role as a probe of the surface structure of the catalyst. From this, a substrate-centric view on catalytic reactions could be obtained using the same characterization methodology as that exploited for interrogating the catalyst. For demonstration, brominated 4-nitrophenol was probed by Br K-edge XAS at different stages of catalytic nitro reduction. Its reactivity was correlated with both the Pt-Au catalyst structure, probed by Pt- and Au-centric XAS, and electrostatic interactions between the substrate and the peptides covering the nanoparticle surfaces. This concept can be extended to operando studies of a large class of catalysts in which surface exposure can be optimized to drive the reaction.
| Original language | English |
|---|---|
| Pages (from-to) | 6757-6761 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry C |
| Volume | 129 |
| Issue number | 14 |
| DOIs | |
| State | Published - Apr 10 2025 |
Funding
This research used beamline 7-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (U.S. DOE, Office of Basic Energy Sciences, Grant No. DE-SC0012335). The authors acknowledge beamline support by L. Ma, D. Li, and A. Tayal.Electron microscopy analysis of A.C.F. and E.A.S. was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012573. Electron microscopy was performed at the Singh Center for Nanotechnology, which is supported by the NSF National Nanotechnology Coordinated Infrastructure Program under grant NNCI-2025608. Additional support for the NSF through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) (DMR-1720530; DMR-2309043). The work was primarily supported by the National Science Foundation under grants 2203858 (A.I.F.) and 2203862 (M.R.K.). This research used beamline 7-BM of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (U.S. DOE, Office of Basic Energy Sciences, Grant No. DE-SC0012335). The authors acknowledge beamline support by L. Ma, D. Li, and A. Tayal.Electron microscopy analysis of A.C.F. and E.A.S. was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012573. Electron microscopy was performed at the Singh Center for Nanotechnology, which is supported by the NSF National Nanotechnology Coordinated Infrastructure Program under grant NNCI-2025608. Additional support for the NSF through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) (DMR-1720530; DMR-2309043). The work was primarily supported by the National Science Foundation under grants 2203858 (A.I.F.) and 2203862 (M.R.K.).