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@ARTICLE{Xiang:857550,
author = {Xiang, Guolei and Tang, Yan and Liu, Zigeng and Zhu, Wei
and Liu, Haitao and Wang, Jiaou and Zhong, Guiming and Li,
Jun and Wang, Xun},
title = {{P}robing {L}igand-{I}nduced {C}ooperative {O}rbital
{R}edistribution {T}hat {D}ominates {N}anoscale
{M}olecule–{S}urface {I}nteractions with
{O}ne-{U}nit-{T}hin {T}i{O} 2 {N}anosheets},
journal = {Nano letters},
volume = {18},
number = {12},
issn = {1530-6992},
address = {Washington, DC},
publisher = {ACS Publ.},
reportid = {FZJ-2018-06541},
pages = {7809-7815},
year = {2018},
abstract = {Understanding the general electronic principles underlying
molecule–surface interactions at the nanoscale is crucial
for revealing the processes based on chemisorption, like
catalysis, surface ligation, surface fluorescence, etc.
However, the electronic mechanisms of how surface states
affect and even dominate the properties of nanomaterials
have long remained unclear. Here, using one-unit-thin TiO2
nanosheet as a model surface platform, we find that surface
ligands can competitively polarize and confine the valence
3d orbitals of surface Ti atoms from delocalized energy band
states to localized chemisorption bonds, through probing the
surface chemical interaction at the orbital level with
near-edge X-ray absorption fine structure (NEXAFS). Such
ligand-induced orbital redistributions, which are revealed
by combining experimental discoveries, quantum calculations,
and theoretical analysis, are cooperative with ligand
coverages and can enhance the strength of chemisorption and
ligation-induced surface effects on nanomaterials. The model
and concept of nanoscale cooperative chemisorption reveal
the general physical principle that drives the
coverage-dependent ligand-induced surface effects on
regulating the electronic structures, surface activity,
optical properties, and chemisorption strength of
nanomaterials.},
cin = {IEK-9},
ddc = {660},
cid = {I:(DE-Juel1)IEK-9-20110218},
pnm = {135 - Fuel Cells (POF3-135)},
pid = {G:(DE-HGF)POF3-135},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:30407013},
UT = {WOS:000453488800051},
doi = {10.1021/acs.nanolett.8b03572},
url = {https://juser.fz-juelich.de/record/857550},
}