10.1021/ja311739v.s001
Ran Long
Ran
Long
Keke Mao
Keke
Mao
Xiaodong Ye
Xiaodong
Ye
Wensheng Yan
Wensheng
Yan
Yaobing Huang
Yaobing
Huang
Jianyong Wang
Jianyong
Wang
Yao Fu
Yao
Fu
Xisheng Wang
Xisheng
Wang
Xiaojun Wu
Xiaojun
Wu
Yi Xie
Yi
Xie
Yujie Xiong
Yujie
Xiong
Surface Facet of Palladium Nanocrystals: A Key Parameter
to the Activation of Molecular Oxygen for Organic Catalysis and Cancer
Treatment
American Chemical Society
2016
cancer treatment materials
reactive singlet O 2.
Pd
O 2 activation
oxidation
facet
singlet O 2.
singlet O 2
electron
surface
ground triplet O 2
O 2 molecules
metal nanocrystals
O 2 activation process
1 O 2 production efficiency
2016-02-19 21:18:23
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Surface_Facet_of_Palladium_Nanocrystals_A_Key_Parameter_to_the_Activation_of_Molecular_Oxygen_for_Organic_Catalysis_and_Cancer_Treatment/2439880
In
many organic reactions, the O<sub>2</sub> activation process
involves a key step where inert ground triplet O<sub>2</sub> is excited
to produce highly reactive singlet O<sub>2</sub>. It remains elusive
what factor induces the change in the electron spin state of O<sub>2</sub> molecules, although it has been discovered that the presence
of noble metal nanoparticles can promote the generation of singlet
O<sub>2</sub>. In this work, we first demonstrate that surface facet
is a key parameter to modulate the O<sub>2</sub> activation process
on metal nanocrystals, by employing single-facet Pd nanocrystals as
a model system. The experimental measurements clearly show that singlet
O<sub>2</sub> is preferentially formed on {100} facets. The simulations
further elucidate that the chemisorption of O<sub>2</sub> to the {100}
facets can induce a spin–flip process in the O<sub>2</sub> molecules,
which is achieved via electron transfer from Pd surface to O<sub>2</sub>. With the capability of tuning O<sub>2</sub> activation, we have
been able to further implement the {100}-faceted nanocubes in glucose
oxidation. It is anticipated that this study will open a door to designing
noble metal nanocatalysts for O<sub>2</sub> activation and organic
oxidation. Another perspective of this work would be the controllability
in tailoring the cancer treatment materials for high <sup>1</sup>O<sub>2</sub> production efficiency, based on the facet control of metal
nanocrystals. In the cases of both organic oxidation and cancer treatment,
it has been exclusively proven that the efficiency of producing singlet
O<sub>2</sub> holds the key to the performance of Pd nanocrystals
in the applications.