A new type of noncovalent surface–π stacking interaction occurring on peroxide-modified titania nanosheets driven by vertical π-state polarization |
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| Authors: | Shenqian Ma Weixin Zhao Jun Zhou Jiaou Wang Shengqi Chu Zigeng Liu Guolei Xiang |
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| Affiliation: | State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029 China.; Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Science, Beijing 100049 China ; Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research Fundamental Electrochemistry (IEK-9), Jülich 52425 Germany |
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| Abstract: | Noncovalent π stacking of aromatic molecules is a universal form of noncovalent interactions normally occurring on planar structures (such as aromatic molecules and graphene) based on sp2-hybridized atoms. Here we reveal a new type of noncovalent surface–π stacking unusually occurring between aromatic groups and peroxide-modified titania (PMT) nanosheets, which can drive versatile aromatic adsorptions. We experimentally explore the underlying electronic-level origin by probing the perturbed changes of unoccupied Ti 3d states with near-edge X-ray absorption fine structures (NEXAFS), and find that aromatic groups can vertically attract π electrons in the surface peroxo-Ti states and increase their delocalization regions. Our discovery updates the concept of noncovalent π-stacking interactions by extending the substrates from carbon-based structures to a transition metal oxide, and presents an approach to exploit the surface chemistry of nanomaterials based on noncovalent interactions.A new type of noncovalent surface–π stacking interaction occurring on a transition metal oxide, titania, is reported, which is different from the traditional forms on sp2-hybridized planar structures like graphene. |
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