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 language | English |
|---|---|
| Pages (from-to) | 26509-26516 |
| Number of pages | 8 |
| Journal | Journal of Physical Chemistry C |
| Volume | 117 |
| Issue number | 50 |
| DOIs | |
| Publication status | Published - 2013 Dec 19 |
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All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Energy(all)
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
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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 journal › Article
TY - JOUR
T1 - A crucial role of bond covalency competition in determining the bandgap and photocatalytic performance of silver oxosalts
AU - Jin, Xiaoyan
AU - Kim, In Young
AU - Jo, Yun Kyung
AU - Bettis, Jerry L.
AU - Koo, Hyun Joo
AU - Whangbo, Myung Hwan
AU - Hwang, Seong Ju
PY - 2013/12/19
Y1 - 2013/12/19
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 .
AB - 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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U2 - 10.1021/jp4101784
DO - 10.1021/jp4101784
M3 - Article
AN - SCOPUS:84890839660
VL - 117
SP - 26509
EP - 26516
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 50
ER -