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Title: Insights into the structure–photoreactivity relationships in well-defined perovskite ferroelectric KNbO 3 nanowires

Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this study, the geometric and electronic structure of perovskite ferroelectric KNbO3 nanowires with respective orthorhombic and monoclinic polymorphs have been systematically addressed. By virtue of aberration-corrected scanning transmission electron microscopy, we directly visualize surface photocatalytic active sites, measure local atomic displacements at an accuracy of several picometers, and quantify ferroelectric polarization combined with first-principles calculations. The photoreactivity of the as-prepared KNbO3 nanowires is assessed toward aqueous rhodamine B degradation under UV light. A synergy between the ferroelectric polarization and electronic structure in photoreactivity enhancement is uncovered, which accounts for the prominent reactivity order: orthorhombic > monoclinic. Additionally, by identifying new photocatalytic products, rhodamine B degradation pathways involving N-deethylation and conjugated structure cleavage are proposed. The findings not only provide new insights into the structure–photoreactivity relationships in perovskite ferroelectric photocatalysts, but also have broad implications in perovskite-based water splitting and photovoltaics, among others.
Authors:
 [1] ;  [2] ;  [3] ;  [3] ;  [4] ;  [5] ;  [2] ;  [2]
  1. National Center for Nanoscience and Technology, Beijing (China); Northeastern Univ., Shenyang (China)
  2. National Center for Nanoscience and Technology, Beijing (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Wuhan Univ. of Technology, Wuhan (China)
  5. Northeastern Univ., Shenyang (China)
Publication Date:
OSTI Identifier:
1222609
Report Number(s):
BNL--108401-2015-JA
Journal ID: ISSN 2041-6520; CSHCBM; R&D Project: CO009; KC0302010
Grant/Contract Number:
51272048
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY