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Research Article

Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling

Guolei Xiang1( )Yang-Gang Wang2
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518000, China
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Graphical Abstract

How size reduction generally enhances nanomaterial surface reactivity has long remained a mysterious fundamental issue. We report an electronic-level insight into this size-reactivity relationship by combining experimental probing and mathematical modeling, from which dual roles of size are revealed.

Abstract

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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Nano Research
Pages 3812-3817
Cite this article:
Xiang G, Wang Y-G. Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling. Nano Research, 2022, 15(4): 3812-3817. https://doi.org/10.1007/s12274-021-3910-1
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Received: 28 August 2021
Revised: 25 September 2021
Accepted: 26 September 2021
Published: 30 October 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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