Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001)

Matthew D. Marcinkowski; Simuck F. Yuk; Nassar Doudin; R. Scott Smith; Manh Thuong Nguyen; Bruce D. Kay; Vassiliki Alexandra Glezakou; Roger Rousseau; Zdenek Dohnálek

doi:10.1021/acscatal.9b03891

Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe₃O₄(001)

Matthew D. Marcinkowski, Simuck F. Yuk, Nassar Doudin, R. Scott Smith, Manh Thuong Nguyen, Bruce D. Kay, Vassiliki Alexandra Glezakou, Roger Rousseau, Zdenek Dohnálek

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

57 Scopus citations

Abstract

Single-atom catalysis has been a topic of increasing interest due to the potential for improved selectivity, reactivity, and catalyst cost. However, single-atom catalysts are still difficult to characterize under realistic reaction conditions, leading to controversy regarding the capabilities of single atoms and a need for model studies. Herein, we examine the reaction of methanol on single Pd atoms supported on Fe₃O₄(001) under ultrahigh vacuum conditions. On Pd-free Fe₃O₄(001), a small fraction of methanol is converted to formaldehyde through a methoxy intermediate at 516 K. The addition of single Pd atoms lowers the barrier to C-H bond cleavage by a factor of 2, resulting in formaldehyde desorption by 290 K. However, Pd atoms begin to sinter by 300 K in the presence of methanol, and Pd clusters do not exhibit the same chemistry. Single atoms significantly lower the barrier to the oxidation of methanol, although their stability remains an issue.

Original language	English
Pages (from-to)	10977-10982
Number of pages	6
Journal	ACS Catalysis
DOIs	https://doi.org/10.1021/acscatal.9b03891
State	Published - 2019
Externally published	Yes

Funding

This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences and performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational Resources were provided by a user proposal at the NERSC user facility located at Lawrence Berkley National Laboratory.

Funders	Funder number
Department of Energy’s Office of Biological and Environmental Research
Office of Basic Energy Sciences
US Department of Energy
Office of Science
Pacific Northwest National Laboratory	PNNL
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

FeO(001)
heterogeneous catalysis
methanol
palladium
partial oxidation
single-atom catalysis

Access to Document

10.1021/acscatal.9b03891

Cite this

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title = "Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001)",

abstract = "Single-atom catalysis has been a topic of increasing interest due to the potential for improved selectivity, reactivity, and catalyst cost. However, single-atom catalysts are still difficult to characterize under realistic reaction conditions, leading to controversy regarding the capabilities of single atoms and a need for model studies. Herein, we examine the reaction of methanol on single Pd atoms supported on Fe3O4(001) under ultrahigh vacuum conditions. On Pd-free Fe3O4(001), a small fraction of methanol is converted to formaldehyde through a methoxy intermediate at 516 K. The addition of single Pd atoms lowers the barrier to C-H bond cleavage by a factor of 2, resulting in formaldehyde desorption by 290 K. However, Pd atoms begin to sinter by 300 K in the presence of methanol, and Pd clusters do not exhibit the same chemistry. Single atoms significantly lower the barrier to the oxidation of methanol, although their stability remains an issue.",

keywords = "FeO(001), heterogeneous catalysis, methanol, palladium, partial oxidation, single-atom catalysis",

author = "Marcinkowski, {Matthew D.} and Yuk, {Simuck F.} and Nassar Doudin and Smith, {R. Scott} and Nguyen, {Manh Thuong} and Kay, {Bruce D.} and Glezakou, {Vassiliki Alexandra} and Roger Rousseau and Zdenek Dohn{\'a}lek",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

doi = "10.1021/acscatal.9b03891",

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journal = "ACS Catalysis",

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T2 - Pd Atoms on Fe3O4(001)

AU - Marcinkowski, Matthew D.

AU - Yuk, Simuck F.

AU - Doudin, Nassar

AU - Smith, R. Scott

AU - Nguyen, Manh Thuong

AU - Kay, Bruce D.

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - Dohnálek, Zdenek

PY - 2019

Y1 - 2019

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AB - Single-atom catalysis has been a topic of increasing interest due to the potential for improved selectivity, reactivity, and catalyst cost. However, single-atom catalysts are still difficult to characterize under realistic reaction conditions, leading to controversy regarding the capabilities of single atoms and a need for model studies. Herein, we examine the reaction of methanol on single Pd atoms supported on Fe3O4(001) under ultrahigh vacuum conditions. On Pd-free Fe3O4(001), a small fraction of methanol is converted to formaldehyde through a methoxy intermediate at 516 K. The addition of single Pd atoms lowers the barrier to C-H bond cleavage by a factor of 2, resulting in formaldehyde desorption by 290 K. However, Pd atoms begin to sinter by 300 K in the presence of methanol, and Pd clusters do not exhibit the same chemistry. Single atoms significantly lower the barrier to the oxidation of methanol, although their stability remains an issue.

KW - FeO(001)

KW - heterogeneous catalysis

KW - methanol

KW - palladium

KW - partial oxidation

KW - single-atom catalysis

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