Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms

Nassar Doudin; Simuck F. Yuk; Matthew D. Marcinkowski; Manh Thuong Nguyen; Jin Cheng Liu; Yang Wang; Zbynek Novotny; Bruce D. Kay; Jun Li; Vassiliki Alexandra Glezakou; Gareth Parkinson; Roger Rousseau; Zdenek Dohnálek

doi:10.1021/acscatal.9b01425

Understanding Heterolytic H₂ Cleavage and Water-Assisted Hydrogen Spillover on Fe₃O₄(001)-Supported Single Palladium Atoms

Nassar Doudin, Simuck F. Yuk, Matthew D. Marcinkowski, Manh Thuong Nguyen, Jin Cheng Liu, Yang Wang, Zbynek Novotny, Bruce D. Kay, Jun Li, Vassiliki Alexandra Glezakou, Gareth Parkinson, Roger Rousseau, Zdenek Dohnálek

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

67 Scopus citations

Abstract

The high specific activity and cost-effectiveness of single-atom catalysts (SACs) hold great promise for numerous catalytic chemistries. In hydrogenation reactions, the mechanisms of critical steps such as hydrogen activation and spillover are far from understood. Here, we employ a combination of scanning tunneling microscopy and density functional theory to demonstrate that on a model SAC comprised of single Pd atoms on Fe₃O₄(001), H₂ dissociates heterolytically between Pd and surface oxygen. The efficient hydrogen spillover allows for continuous hydrogenation to high coverages, which ultimately leads to the lifting of Fe₃O₄ reconstruction and Pd reduction and destabilization. Water plays an important role in reducing the proton diffusion barrier, thereby facilitating the redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H₂ activation mechanism on single Pd atoms and corroborates the importance of charge transport on reducible support away from the active site.

Original language	English
Pages (from-to)	7876-7887
Number of pages	12
Journal	ACS Catalysis
Volume	9
Issue number	9
DOIs	https://doi.org/10.1021/acscatal.9b01425
State	Published - Sep 6 2019
Externally published	Yes

Funding

This work was supported by the U.S. Department of Energy, 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. J.-C.L. and J.L. were financially sponsored by the National Natural Science Foundation of China (NSFC grants 21590792 and 91645203). G.P. acknowledges funding from the Austrian Science Fund START prize Y 847-N20. J.-C.L. is grateful to the Alternative-Sponsor Fellowship (ASF) at PNNL.

Funders	Funder number
Austrian Science Fund START	Y 847-N20
Office of Basic Energy Sciences
Office of Biological and Environmental Research
U.S. Department of Energy
Pacific Northwest National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division
National Natural Science Foundation of China	21590792, 91645203

Keywords

FeO(001)
dissociative adsorption
hydrogen
kinetic barriers
palladium
single-atom catalyst

Access to Document

10.1021/acscatal.9b01425

Cite this

Doudin, N., Yuk, S. F., Marcinkowski, M. D., Nguyen, M. T., Liu, J. C., Wang, Y., Novotny, Z., Kay, B. D., Li, J., Glezakou, V. A., Parkinson, G., Rousseau, R., & Dohnálek, Z. (2019). Understanding Heterolytic H₂ Cleavage and Water-Assisted Hydrogen Spillover on Fe₃O₄(001)-Supported Single Palladium Atoms. ACS Catalysis, 9(9), 7876-7887. https://doi.org/10.1021/acscatal.9b01425

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abstract = "The high specific activity and cost-effectiveness of single-atom catalysts (SACs) hold great promise for numerous catalytic chemistries. In hydrogenation reactions, the mechanisms of critical steps such as hydrogen activation and spillover are far from understood. Here, we employ a combination of scanning tunneling microscopy and density functional theory to demonstrate that on a model SAC comprised of single Pd atoms on Fe3O4(001), H2 dissociates heterolytically between Pd and surface oxygen. The efficient hydrogen spillover allows for continuous hydrogenation to high coverages, which ultimately leads to the lifting of Fe3O4 reconstruction and Pd reduction and destabilization. Water plays an important role in reducing the proton diffusion barrier, thereby facilitating the redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H2 activation mechanism on single Pd atoms and corroborates the importance of charge transport on reducible support away from the active site.",

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AU - Nguyen, Manh Thuong

AU - Liu, Jin Cheng

AU - Wang, Yang

AU - Novotny, Zbynek

AU - Kay, Bruce D.

AU - Li, Jun

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AU - Rousseau, Roger

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AB - The high specific activity and cost-effectiveness of single-atom catalysts (SACs) hold great promise for numerous catalytic chemistries. In hydrogenation reactions, the mechanisms of critical steps such as hydrogen activation and spillover are far from understood. Here, we employ a combination of scanning tunneling microscopy and density functional theory to demonstrate that on a model SAC comprised of single Pd atoms on Fe3O4(001), H2 dissociates heterolytically between Pd and surface oxygen. The efficient hydrogen spillover allows for continuous hydrogenation to high coverages, which ultimately leads to the lifting of Fe3O4 reconstruction and Pd reduction and destabilization. Water plays an important role in reducing the proton diffusion barrier, thereby facilitating the redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H2 activation mechanism on single Pd atoms and corroborates the importance of charge transport on reducible support away from the active site.

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