Mechanistic
Insights into Photocatalyzed Hydrogen
Desorption from Palladium Surfaces Assisted by Localized Surface Plasmon
Resonances
Version 2 2018-03-23, 20:45
Version 1 2018-03-23, 20:43
Posted on 2018-03-23 - 20:45
Nanoparticles synthesized
from plasmonic metals can absorb low-energy
light, producing an oscillation/excitation of their valence electron
density that can be utilized in chemical conversions. For example,
heterogeneous photocatalysis can be achieved within heterometallic
antenna-reactor complexes (HMARCs), by coupling a reactive center
at which a chemical reaction occurs to a plasmonic nanoparticle that
acts as a light-absorbing antenna. For example, HMARCs composed of
aluminum antennae and palladium (Pd) reactive centers have been demonstrated
recently to catalyze selective hydrogenation of acetylene to ethylene.
Here, we explore within a theoretical framework the rate-limiting
step of hydrogen photodesorption from a Pd surfacecrucial
to achieving partial rather than full hydrogenation of acetyleneto
understand the mechanism behind the photodesorption process within
the HMARC assembly. To properly describe electronic excited states
of the metal–molecule system, we employ embedded complete active
space self-consistent field and n-electron valence
state perturbation theory to second order within density functional
embedding theory. The results of these calculations reveal that the
photodesorption mechanism does not create a frequently invoked transient
negative ion species but instead enhances population of available
excited-state, low-barrier pathways that exhibit negligible charge-transfer
character.
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Spata, Vincent
A.; Carter, Emily A. (2018). Mechanistic
Insights into Photocatalyzed Hydrogen
Desorption from Palladium Surfaces Assisted by Localized Surface Plasmon
Resonances. ACS Publications. Collection. https://doi.org/10.1021/acsnano.8b00352
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AUTHORS (2)
VS
Vincent
A. Spata
EC
Emily A. Carter
KEYWORDS
charge-transfer characterlight-absorbing antennalow-energy lighthydrogenationphotodesorption processreactive centerhydrogen photodesorptionplasmonic nanoparticleion speciesPdPalladium Surfaces Assistedphotodesorption mechanismMechanistic Insightsvalence electron densityrate-limiting stepembedding theorylow-barrier pathwaysreactive centerschemical reactionelectron valence state perturbation theoryheterometallic antenna-reactor complexesacetyleneplasmonic metalsPhotocatalyzed Hydrogen DesorptionHMARC assemblyaluminum antennaeLocalized Surface Plasmon Resonances Nanoparticleschemical conversions