Header

UZH-Logo

Maintenance Infos

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


Doudin, Nassar; Yuk, Simuck F; Marcinkowski, Matthew D; Nguyen, Manh-Thuong; Liu, Jin-Cheng; Wang, Yang; Novotny, Zbynek; Kay, Bruce D; Li, Jun; Glezakou, Vassiliki-Alexandra; Parkinson, Gareth; Rousseau, Roger; Dohnálek, Zdenek (2019). Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms. ACS Catalysis, 9(9):7876-7887.

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.

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.

Statistics

Citations

Dimensions.ai Metrics
26 citations in Web of Science®
24 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

1 download since deposited on 17 Oct 2019
0 downloads since 12 months
Detailed statistics

Additional indexing

Item Type:Journal Article, not_refereed, original work
Communities & Collections:07 Faculty of Science > Physics Institute
Dewey Decimal Classification:530 Physics
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Language:English
Date:6 September 2019
Deposited On:17 Oct 2019 06:01
Last Modified:29 Jul 2020 11:28
Publisher:American Chemical Society (ACS)
ISSN:2155-5435
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acscatal.9b01425

Download

Closed Access: Download allowed only for UZH members