Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters
Abstract
Copper surfaces display high catalytic selectivity but have poor hydrogen dissociation kinetics; therefore, we consider icosahedral Cu13 nanoclusters to understand how nanoscale structure might improve catalytic prospects. We find that the spin state is a surprisingly important design consideration. Cu13 clusters have large magnetic moments due to finite size and symmetry effects and exhibit magnetization-dependent catalytic behavior. The most favorable transition state for hydrogen dissociation has a lower activation energy than that on single-crystal copper surfaces but requires a magnetization switch from 5 to 3 μB. Without this switch, the activation energy is higher than that on single-crystal surfaces. Weak spin–orbit coupling hinders this switch, decreasing the kinetic rate of hydrogen dissociation by a factor of 16. Here, we consider strategies to facilitate magnetization switches through optical excitations, substitution, charge states, and co-catalysts; these considerations demonstrate how control of magnetic properties could improve catalytic performance.
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1597695
- Grant/Contract Number:
- SC0012573
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 18; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dissociation; Activation energy; Magnetic properties; Nanoclusters; Mathematical methods
Citation Formats
Hoyt, Robert A., Montemore, Matthew M., and Kaxiras, Efthimios. Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.8b02133.
Hoyt, Robert A., Montemore, Matthew M., & Kaxiras, Efthimios. Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters. United States. https://doi.org/10.1021/acs.jpclett.8b02133
Hoyt, Robert A., Montemore, Matthew M., and Kaxiras, Efthimios. Sat .
"Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters". United States. https://doi.org/10.1021/acs.jpclett.8b02133. https://www.osti.gov/servlets/purl/1597695.
@article{osti_1597695,
title = {Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters},
author = {Hoyt, Robert A. and Montemore, Matthew M. and Kaxiras, Efthimios},
abstractNote = {Copper surfaces display high catalytic selectivity but have poor hydrogen dissociation kinetics; therefore, we consider icosahedral Cu13 nanoclusters to understand how nanoscale structure might improve catalytic prospects. We find that the spin state is a surprisingly important design consideration. Cu13 clusters have large magnetic moments due to finite size and symmetry effects and exhibit magnetization-dependent catalytic behavior. The most favorable transition state for hydrogen dissociation has a lower activation energy than that on single-crystal copper surfaces but requires a magnetization switch from 5 to 3 μB. Without this switch, the activation energy is higher than that on single-crystal surfaces. Weak spin–orbit coupling hinders this switch, decreasing the kinetic rate of hydrogen dissociation by a factor of 16. Here, we consider strategies to facilitate magnetization switches through optical excitations, substitution, charge states, and co-catalysts; these considerations demonstrate how control of magnetic properties could improve catalytic performance.},
doi = {10.1021/acs.jpclett.8b02133},
journal = {Journal of Physical Chemistry Letters},
number = 18,
volume = 9,
place = {United States},
year = {Sat Aug 25 00:00:00 EDT 2018},
month = {Sat Aug 25 00:00:00 EDT 2018}
}
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Works referencing / citing this record:
Ligand functionalized copper nanoclusters for versatile applications in catalysis, sensing, bioimaging, and optoelectronics
journal, January 2019
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