@article{f95887861ef74129af310d5e286af3ad,
title = "Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers",
abstract = "Atomically thin platinum (Pt) shells on titanium tungsten carbide (TiWC) and titanium tungsten nitride (TiWN) core nanoparticles display substantially modified catalytic performance compared to commercial Pt nanoparticles. In situ X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses indicate these differences are primarily caused by ligand effects from the hybridization of Pt and W d states at the core-shell interface. The heterometallic bonding between the shell and the core elements leads to broadening of the Pt valence d-band, a downshift of the d-band center, and greatly reduced adsorbate binding energies, as verified by density functional theory calculations and microcalorimetry of CO adsorption. In situ XANES measurements during reduction treatment demonstrated how surface oxides disrupt the bonding interactions between Pt and W. Changes to the Pt electronic structure from different core materials correlated with ethylene hydrogenation reactivity, where increased Pt d-band broadening was associated with weaker adsorbate binding and consequently lower turnover frequency. The significant electronic structure modification of Pt by the TiWC and TiWN cores exemplifies how core-shell nanoparticle architectures can be used to tune catalyst reactivity.",
author = "Aaron Garg and Goncalves, {Danielle S.} and Yusu Liu and Zhenshu Wang and Linxi Wang and Yoo, {Jong Suk} and Alexie Kolpak and Rioux, {Robert M.} and Daniela Zanchet and Yuriy Rom{\'a}n-Leshkov",
note = "Funding Information: This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences (DE- SC0016214). D.S.G. and D.Z. acknowledge funding by the S{\~a}o Paulo Research Foundation (FAPESP 2015/23900-2 and 2015/50375-6) and the National Council of Technological and Scientific Development (CNPq 309373/2014-0 and D.S.G. Ph.D. scholarship CNPq 140547/2017-7). This study was also financed in part by the Coordination for the Improvement of Higher Education Personnel (CAPES)–Finance Code 001, Brazil. L.W. and R.M.R. acknowledge support from the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, and Biosciences Division, Catalysis Sciences Program under grant number DE-SC0016192. We thank the MISTI-Brazil grant for travel support. The authors thank T.E.R. Fiuza for her help during the XANES/EXAFS data collection. This research used resources of the Advanced Photon Source, a U.S. DOE, Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 (12-BM-B beamline, GUP 55290). Computations were performed using computational resources from the Extreme Science and Engineering Discovery Environment (XSEDE) and the National Energy Research Scientific Computing Center (NERSC). Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",
year = "2019",
month = aug,
day = "2",
doi = "10.1021/acscatal.9b01272",
language = "English (US)",
volume = "9",
pages = "7090--7098",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "8",
}