Abstract
Synchrotron spectroscopy and Density Functional Theory (DFT) are combined to develop a new descriptor for the stability of adsorbed chemical intermediates on metal alloy surfaces. This descriptor probes the separation of occupied and unoccupied d electron density in platinum and is related to shifts in Resonant Inelastic X-ray Scattering (RIXS) signals. Simulated and experimental spectroscopy are directly compared to show that the promoter metal identity controls the orbital shifts in platinum electronic structure. The associated RIXS features are correlated with the differences in the band centers of the occupied and unoccupied d bands, providing chemical intuition for the alloy ligand effect and providing a connection to traditional descriptions of chemisorption. The ready accessibility of this descriptor to both DFT calculations and experimental spectroscopy, and its connection to chemisorption, allow for deeper connections between theory and characterization in the discovery of new catalysts.
| Original language | English |
|---|---|
| Pages (from-to) | 11216-11226 |
| Number of pages | 11 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 25 |
| Issue number | 16 |
| DOIs | |
| State | Published - Mar 31 2023 |
| Externally published | Yes |
Funding
BCB, SCP, ECW, ZW, GZ, JTM, and J G acknowledge support by the National Science Foundation under Cooperative Agreement No. EEC-1647722. Use of the Center for Nanoscale Materials, a U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility under Contract No. DE-AC02-06CH11357, and of computational resources from the National Energy Research Scientific Computing Center. Use of the advanced photon source was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. MRCAT operations, beamline 10-BM and 10-ID, are supported by the Department of Energy and the MRCAT member institutions. The authors also acknowledge the use of the 11-ID-C beamline at the advanced photon source. AJK acknowledges the support of the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, Catalysis Science Program under contract No. DE-AC-02-06CH11357. XPS data was collected at the Surface Analysis Facility of the Birck Nanotechnology Center of Purdue University.