Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Nonadiabatic Hydrogen Dissociation on Copper Nanoclusters

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [2]
  1. Harvard Univ., Cambridge, MA (United States); Harvard University
  2. Harvard Univ., Cambridge, MA (United States)
+ Show Author Affiliations

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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012573
OSTI ID:
1597695
Alternate ID(s):
OSTI ID: 1539342
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 18 Vol. 9; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (22)

Reversible work transition state theory: application to dissociative adsorption of hydrogen journal February 1995
Adsorption and desorption dynamics as seen through molecular beam techniques journal January 1994
Surface Magnetism of Cobalt Nanoislands Controlled by Atomic Hydrogen journal December 2016
Size Dependent Catalytic Activity of Reusable Subnanometer Copper(0) Clusters journal July 2012
Catalytic Activity of Single Transition-Metal Atom Doped in Cu(111) Surface for Heterogeneous Hydrogenation journal July 2013
Reactivity of Fe n , Co n , and Cu n Clusters with O 2 and D 2 Studied at Single-Collision Conditions journal January 1996
s-Electron Ferromagnetism in Gold and Silver Nanoclusters journal October 2007
Why gold is the noblest of all the metals journal July 1995
Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters journal January 2016
Nanoclusters Synthesized by Synchrotron Radiolysis in Concert with Wet Chemistry journal November 2014
Synthesis, structure and properties of metal nanoclusters journal January 2006
Amorphous structures of Cu, Ag, and Au nanoclusters from first principles calculations journal December 2002
Surface reactions of metal clusters. II. Reactivity surveys with D 2 , N 2 , and CO journal September 1985
Hydrogen-mediated long-range magnetic ordering in Pd-rich alloy film journal January 2015
The SIESTA method for ab initio order- N materials simulation journal March 2002
On-site approximation for spin–orbit coupling in linear combination of atomic orbitals density functional methods journal November 2007
Ab initio random structure search for 13-atom clusters of fcc elements journal February 2013
Structures of 13-atom clusters of fcc transition metals by ab initio and semiempirical calculations journal November 2006
Spin-orbit splitting of the Shockley surface state on Cu(111) journal February 2013
Spin-Flip Transitions Induced by Time-Dependent Electric Fields in Surfaces with Strong Spin-Orbit Interaction journal October 2012
Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations journal March 2012
R EACTIONS OF T RANSITION M ETAL C LUSTERS WITH S MALL M OLECULES journal October 1999

Cited By (2)

Ligand functionalized copper nanoclusters for versatile applications in catalysis, sensing, bioimaging, and optoelectronics journal January 2019
Impurity diffusion induced dynamic electron donors in semiconductors journal October 2019

Similar Records

CO–induced roughening of Cu(111): formation and detection of reactive nanoclusters on metal surfaces
Journal Article · Thu Nov 21 19:00:00 EST 2024 · Surface Science · OSTI ID:3012302
Atomically Precise Metal Nanoclusters for Catalytic Application
Technical Report · Thu Nov 17 23:00:00 EST 2016 · OSTI ID:1332684
Simulation of the processes of structuring of copper nanoclusters in terms of the tight-binding potential
Journal Article · Fri May 15 00:00:00 EDT 2009 · Journal of Experimental and Theoretical Physics · OSTI ID:21246897

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Activation energy
Dissociation
Magnetic properties
Mathematical methods
Nanoclusters