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

Xiang，Guolei1; Wang，Yang Gang2

2021

10.1007/s12274-021-3910-1

Nano Research   影响因子和分区

1998-0124

1998-0000

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 HO-TiO 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. [Figure not available: see fulltext.]

chemisorption strength electronic mechanism size effect surface coordination bond surface reactivity

SCI ; EI

英语

其他

National Natural Science Foundation of China[21801012]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied

WOS:000712941900005

TSINGHUA UNIV PRESS

20214411106558

Bond strength (chemical) ; Nanostructured materials ; Quantum chemistry ; Reduction ; Size determination ; Titanium dioxide

Nanotechnology:761 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Inorganic Compounds:804.2 ; Crystalline Solids:933.1

2-s2.0-85118240755

Scopus

1.State Key Laboratory of Chemical Resource Engineering,College of Chemistry,Beijing University of Chemical Technology,Beijing,100029,China
2.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518000,China

Xiang，Guolei,Wang，Yang Gang. Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling[J]. Nano Research,2021,15:3812-3817.

Xiang，Guolei,&Wang，Yang Gang.(2021).Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling.Nano Research,15,3812-3817.

Xiang，Guolei,et al."Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling".Nano Research 15(2021):3812-3817.