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Size reduction can generally enhance the surface reactivity of inorganic nanomaterials. The origin of this nano-effect has been ascribed to ultrasmall size, large specific surface area, or abundant defects, but the most intrinsic electronic-level principles are still not fully understood yet. By combining experimental explorations and mathematical modeling, herein we propose an electronic-level model to reveal the physicochemical nature of size-dependent nanomaterial surface reactivity. Experimentally, we reveal that competitive redistribution of surface atomic orbitals from extended energy band states into localized surface chemical bonds is the critical electronic process of surface chemical interactions, using H2O2-TiO2 chemisorption as a model reaction. Theoretically, we define a concept, orbital potential (G), to describe the electronic feature determining the tendency of orbital redistribution, and deduce a mathematical model to reveal how size modulates surface reactivity. We expose the dual roles of size reduction in enhancing nanomaterial surface reactivity—inversely correlating to orbital potential and amplifying the effects of other structural factors on surface reactivity.

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Publication history

Received: 28 August 2021
Revised: 25 September 2021
Accepted: 26 September 2021
Published: 30 October 2021
Issue date: April 2022

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© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This research was supported by the National Natural Science Foundation of China (No. 21801012).

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Reprints and Permission requests may be sought directly from editorial office.
Email: nanores@tup.tsinghua.edu.cn

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