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Adsorbate-driven reactive interfacial Pt-NiO_1-x nanostructure formation on the Pt₃Ni(111) alloy surface.

ABSTRACT: The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nanostructures are then formed under chemical reaction environments at ambient pressure, which thus increases the catalytic activity for the CO oxidation reaction. Our in situ surface characterizations using ambient-pressure scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy exhibit (i) a Pt-skin layer on the Pt-Ni alloyed surface under ultrahigh vacuum, (ii) selective Ni segregation followed by the formation of NiO_1-x clusters under oxygen gas, and (iii) the coexistence of NiO_1-x clusters on the Pt-skin during the CO oxidation reaction. The formation of interfacial Pt-NiO_1-x nanostructures is responsible for a highly efficient step in the CO oxidation reaction. Density functional theory calculations of the Pt₃Ni(111) surface demonstrate that a CO molecule adsorbed on an exposed Pt atom with an interfacial oxygen from a segregated NiO_1-x cluster has a low surface energy barrier of 0.37 eV, compared with 0.86 eV for the Pt(111) surface.

SUBMITTER: Kim J

PROVIDER: S-EPMC6044734 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Publications

Adsorbate-driven reactive interfacial Pt-NiO1-x nanostructure formation on the Pt3Ni(111) alloy surface.

Kim Jeongjin J Park Woong Hyeon WH Doh Won Hui WH Lee Si Woo SW Noh Myung Cheol MC Gallet Jean-Jacques JJ Bournel Fabrice F Kondoh Hiroshi H Mase Kazuhiko K Jung Yousung Y Mun Bongjin Simon BS Park Jeong Young JY

Science advances 20180713 7

The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nan ...[more]

PMID: 30027118

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Project description:Accurately modeling heterogeneous catalysis requires accurate descriptions of rate-controlling elementary reactions of molecules on metal surfaces, but standard density functionals (DFs) are not accurate enough for this. The problem can be solved with the specific reaction parameter approach to density functional theory (SRP-DFT), but the transferability of SRP DFs among chemically related systems is limited. We combine the MS-PBEl, MS-B86bl, and MS-RPBEl semilocal made simple (MS) meta-generalized gradient approximation (GGA) (mGGA) DFs with rVV10 nonlocal correlation, and we evaluate their performance for the hydrogen (H2) + Cu(111), deuterium (D2) + Ag(111), H2 + Au(111), and D2 + Pt(111) gas-surface systems. The three MS mGGA DFs that have been combined with rVV10 nonlocal correlation were not fitted to reproduce particular experiments, nor has the b parameter present in rVV10 been reoptimized. Of the three DFs obtained the MS-PBEl-rVV10 DF yields an excellent description of van der Waals well geometries. The three original MS mGGA DFs gave a highly accurate description of the metals, which was comparable in quality to that obtained with the PBEsol DF. Here, we find that combining the three original MS mGGA DFs with rVV10 nonlocal correlation comes at the cost of a slightly less accurate description of the metal. However, the description of the metal obtained in this way is still better than the descriptions obtained with SRP DFs specifically optimized for individual systems. Using the Born-Oppenheimer static surface (BOSS) model, simulations of molecular beam dissociative chemisorption experiments yield chemical accuracy for the D2 + Ag(111) and D2 + Pt(111) systems. A comparison between calculated and measured E 1/2(ν, J) parameters describing associative desorption suggests chemical accuracy for the associative desorption of H2 from Au(111) as well. Our results suggest that ascending Jacob's ladder to the mGGA rung yields increasingly more accurate results for gas-surface reactions of H2 (D2) interacting with late transition metals.

Dataset Information

Adsorbate-driven reactive interfacial Pt-NiO_1-x nanostructure formation on the Pt₃Ni(111) alloy surface.

Publications

Adsorbate-driven reactive interfacial Pt-NiO<sub>1-<i>x</i></sub> nanostructure formation on the Pt<sub>3</sub>Ni(111) alloy surface.

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