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

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 com...

Full description

Saved in:
Bibliographic Details
Published in:Nano research 2022-04, Vol.15 (4), p.3812-3817
Main Authors: Xiang, Guolei, Wang, Yang-Gang
Format: Article
Language:English
Subjects:
Atomic/Molecular Structure and Spectra
Biomedicine
Biotechnology
Chemical bonds
Chemical interactions
Chemisorption
Chemistry and Materials Science
Condensed Matter Physics
Energy bands
Hydrogen peroxide
Materials Science
Mathematical analysis
Mathematical models
Nanomaterials
Nanotechnology
Principles
Reactivity
Research Article
Size reduction
Titanium dioxide
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 H 2 O 2 -TiO 2 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.
ISSN:1998-0124
1998-0000
DOI:10.1007/s12274-021-3910-1