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

Abstract

The high specific activity, novel properties, and cost effectiveness of single-atom catalysts (SAC) hold great promise and allow for new chemistry in numerous reactions. Here, we focus on fundamental understanding of the critical step in hydrogenation reactions, H2 activation, on a model SAC catalyst comprised of single Pd atoms on reconstructed Fe3O4(001). Using a combination of scanning tunneling microscopy and density functional theory we demonstrate that H2 dissociates heterolytically, ultimately yielding hydroxyls on, and excess charge in, the Fe3O4 support. The hydrogenation can be carried out to high coverages and ultimately leads to lifting of the Fe3O4 reconstruction and Pd reduction and destabilization. Water plays an important role in reduction of the hydrogen diffusion barrier, thereby facilitating redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H2 activation mechanism on single Pd atoms and shows the importance of a reducible support that can facilitate charge transport away from the active site.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [3];  [1]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. Tsinghua University
  3. VISITORS
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1566303
Report Number(s):
PNNL-SA-141193
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9
Country of Publication:
United States
Language:
English

Citation Formats

Doudin, Nassar M., 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 S., Rousseau, Roger J., and Dohnalek, Zdenek. Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b01425.
Doudin, Nassar M., 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 S., Rousseau, Roger J., & Dohnalek, Zdenek. Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms. United States. doi:10.1021/acscatal.9b01425.
Doudin, Nassar M., 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 S., Rousseau, Roger J., and Dohnalek, Zdenek. Fri . "Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms". United States. doi:10.1021/acscatal.9b01425.
@article{osti_1566303,
title = {Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms},
author = {Doudin, Nassar M. and Yuk, Simuck F. and Marcinkowski, Matthew D. and Nguyen, Manh Thuong and Liu, Jin-Cheng and Wang, Yang and Novotny, Zbynek and Kay, Bruce D. and Li, Jun and Glezakou, Vassiliki-Alexandra and Parkinson, Gareth S. and Rousseau, Roger J. and Dohnalek, Zdenek},
abstractNote = {The high specific activity, novel properties, and cost effectiveness of single-atom catalysts (SAC) hold great promise and allow for new chemistry in numerous reactions. Here, we focus on fundamental understanding of the critical step in hydrogenation reactions, H2 activation, on a model SAC catalyst comprised of single Pd atoms on reconstructed Fe3O4(001). Using a combination of scanning tunneling microscopy and density functional theory we demonstrate that H2 dissociates heterolytically, ultimately yielding hydroxyls on, and excess charge in, the Fe3O4 support. The hydrogenation can be carried out to high coverages and ultimately leads to lifting of the Fe3O4 reconstruction and Pd reduction and destabilization. Water plays an important role in reduction of the hydrogen diffusion barrier, thereby facilitating redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H2 activation mechanism on single Pd atoms and shows the importance of a reducible support that can facilitate charge transport away from the active site.},
doi = {10.1021/acscatal.9b01425},
journal = {ACS Catalysis},
number = 9,
volume = 9,
place = {United States},
year = {2019},
month = {9}
}