In situ spectroscopy and mechanistic insights into CO oxidation on transition-metal-substituted ceria nanoparticles

Joseph S. Elias; Kelsey A. Stoerzinger; Wesley T. Hong; Marcel Risch; Livia Giordano; Azzam N. Mansour; Yang Shao-Horn

doi:10.1021/acscatal.7b01600

In situ spectroscopy and mechanistic insights into CO oxidation on transition-metal-substituted ceria nanoparticles

Joseph S. Elias, Kelsey A. Stoerzinger, Wesley T. Hong, Marcel Risch, Livia Giordano, Azzam N. Mansour, Yang Shao-Horn

Research output: Contribution to journal › Article › peer-review

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Abstract

Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu_0.1Ce_0.9O_2-x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M_0.1Ce_0.9O_2-x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2-transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu_0.1Ce_0.9O_2-x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO₃^2- in the absence of O₂. We find that CO₃^2- desorbs as CO₂ only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O₂. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper-oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is ratedetermining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (E_vac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M_0.1Ce_0.9O_2-x catalysts that spans three orders of magnitude. The applicability of E_vac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu_0.1La_0.1Ce_0.8O_2-x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO₂ materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting metal through the computational screening of E_vac.

Original language	English (US)
Pages (from-to)	6843-6857
Number of pages	15
Journal	ACS Catalysis
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.7b01600
State	Published - Oct 6 2017
Externally published	Yes

Bibliographical note

Funding Information:
Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. The ALS is supported by the Director, Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231. DFT computations in this work were benefited from the use 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. This work was partially supported by Philip Morris International. J.S.E. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1122374. The authors would like to thank the staff scientists at beamlines X11A at NSLS and 9.3.2 at ALS and Dr. John Heinzel (Naval Surface Warfare Center) for help with the in situ XAS measurements.

Publisher Copyright:
© 2017 American Chemical Society.

Keywords

Ambient pressure xps
Catalysis
Ceria
DFT
In situ spectroscopy
Mechanisms of reactions
Nanotechnology

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title = "In situ spectroscopy and mechanistic insights into CO oxidation on transition-metal-substituted ceria nanoparticles",

abstract = "Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2-x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2-transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2-x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32- in the absence of O2. We find that CO32- desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper-oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is ratedetermining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2-x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2-x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting metal through the computational screening of Evac.",

keywords = "Ambient pressure xps, Catalysis, Ceria, DFT, In situ spectroscopy, Mechanisms of reactions, Nanotechnology",

author = "Elias, {Joseph S.} and Stoerzinger, {Kelsey A.} and Hong, {Wesley T.} and Marcel Risch and Livia Giordano and Mansour, {Azzam N.} and Yang Shao-Horn",

note = "Funding Information: Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. The ALS is supported by the Director, Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231. DFT computations in this work were benefited from the use 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. This work was partially supported by Philip Morris International. J.S.E. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1122374. The authors would like to thank the staff scientists at beamlines X11A at NSLS and 9.3.2 at ALS and Dr. John Heinzel (Naval Surface Warfare Center) for help with the in situ XAS measurements. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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T1 - In situ spectroscopy and mechanistic insights into CO oxidation on transition-metal-substituted ceria nanoparticles

AU - Elias, Joseph S.

AU - Stoerzinger, Kelsey A.

AU - Hong, Wesley T.

AU - Risch, Marcel

AU - Giordano, Livia

AU - Mansour, Azzam N.

AU - Shao-Horn, Yang

N1 - Funding Information: Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. The ALS is supported by the Director, Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231. DFT computations in this work were benefited from the use 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. This work was partially supported by Philip Morris International. J.S.E. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1122374. The authors would like to thank the staff scientists at beamlines X11A at NSLS and 9.3.2 at ALS and Dr. John Heinzel (Naval Surface Warfare Center) for help with the in situ XAS measurements. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/10/6

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N2 - Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2-x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2-transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2-x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32- in the absence of O2. We find that CO32- desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper-oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is ratedetermining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2-x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2-x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting metal through the computational screening of Evac.

AB - Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2-x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2-transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2-x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32- in the absence of O2. We find that CO32- desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper-oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is ratedetermining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2-x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2-x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting metal through the computational screening of Evac.

KW - Ambient pressure xps

KW - Catalysis

KW - Ceria

KW - DFT

KW - In situ spectroscopy

KW - Mechanisms of reactions

KW - Nanotechnology

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In situ spectroscopy and mechanistic insights into CO oxidation on transition-metal-substituted ceria nanoparticles

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Keywords

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