A crucial role of bond covalency competition in determining the bandgap and photocatalytic performance of silver oxosalts

Xiaoyan Jin, In Young Kim, Yun Kyung Jo, Jerry L. Bettis, Hyun Joo Koo, Myung Hwan Whangbo, Seong Ju Hwang

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The optical bandgaps, the surface charges, and the photocatalytic activities of the silver oxosalts Ag 3 AsO 4 , Ag 2 CO 3 , Ag 3 PO 4 , Ag 2 SO 4 , and Ag 2 SeO 4 are systematically investigated with several experimental techniques and first principles density functional theory calculations. The trends in the optical bandgaps and the surface charges of these silver oxosalts, Ag x (XO y ) z , are analyzed by considering how the X-O bond covalency affects the charge on the terminal oxygen atoms and the Ag-O bond covalency. The optical bandgaps of Ag x (XO y ) z are well-described by the bond-covalency competition in the Ag-O-X linkages because an increase in the overlap between the O 2s/2p and X ns/np orbitals decreases the overlap between the Ag 4d and O 2s/2p orbitals. The optical bandgap increases linearly with increasing the Z/r ratio of the atom X, a simple measure of the X-O bond covalency. In the photodegradation of charged molecules, the surface charge of Ag x (XO y ) z plays a prominent role and decreases with increasing the Z/r ratio. As expected from the present theoretical predictions, newly investigated Ag 2 SeO 4 exhibits a promising photocatalytic activity under visible light. The Z/r ratio of the central atom X provides an effective measure for predicting the photocatalyst performance and the optical bandgap of silver oxosalts Ag x (XO y ) z .

Original languageEnglish
Pages (from-to)26509-26516
Number of pages8
JournalJournal of Physical Chemistry C
Volume117
Issue number50
DOIs
Publication statusPublished - 2013 Dec 19

Fingerprint

Optical band gaps
Silver
Energy gap
silver
Surface charge
Atoms
orbitals
Photodegradation
Carbon Monoxide
Photocatalysts
linkages
Density functional theory
atoms
oxygen atoms
Oxygen
density functional theory
trends
Molecules
predictions
molecules

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Jin, Xiaoyan ; Kim, In Young ; Jo, Yun Kyung ; Bettis, Jerry L. ; Koo, Hyun Joo ; Whangbo, Myung Hwan ; Hwang, Seong Ju. / A crucial role of bond covalency competition in determining the bandgap and photocatalytic performance of silver oxosalts. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 50. pp. 26509-26516.
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A crucial role of bond covalency competition in determining the bandgap and photocatalytic performance of silver oxosalts. / Jin, Xiaoyan; Kim, In Young; Jo, Yun Kyung; Bettis, Jerry L.; Koo, Hyun Joo; Whangbo, Myung Hwan; Hwang, Seong Ju.

In: Journal of Physical Chemistry C, Vol. 117, No. 50, 19.12.2013, p. 26509-26516.

Research output: Contribution to journalArticle

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AU - Jin, Xiaoyan

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N2 - The optical bandgaps, the surface charges, and the photocatalytic activities of the silver oxosalts Ag 3 AsO 4 , Ag 2 CO 3 , Ag 3 PO 4 , Ag 2 SO 4 , and Ag 2 SeO 4 are systematically investigated with several experimental techniques and first principles density functional theory calculations. The trends in the optical bandgaps and the surface charges of these silver oxosalts, Ag x (XO y ) z , are analyzed by considering how the X-O bond covalency affects the charge on the terminal oxygen atoms and the Ag-O bond covalency. The optical bandgaps of Ag x (XO y ) z are well-described by the bond-covalency competition in the Ag-O-X linkages because an increase in the overlap between the O 2s/2p and X ns/np orbitals decreases the overlap between the Ag 4d and O 2s/2p orbitals. The optical bandgap increases linearly with increasing the Z/r ratio of the atom X, a simple measure of the X-O bond covalency. In the photodegradation of charged molecules, the surface charge of Ag x (XO y ) z plays a prominent role and decreases with increasing the Z/r ratio. As expected from the present theoretical predictions, newly investigated Ag 2 SeO 4 exhibits a promising photocatalytic activity under visible light. The Z/r ratio of the central atom X provides an effective measure for predicting the photocatalyst performance and the optical bandgap of silver oxosalts Ag x (XO y ) z .

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