Thermally Stable N_2-Intercalated WO_3 Photoanodes for Water Oxidation
Abstract
We describe stable intercalation compounds of the composition xN_2•WO_3 (x = 0.034–0.039), formed by trapping N_2 in WO_3. The incorporation of N_2 significantly reduced the absorption threshold of WO_3; notably, 0.039N_2•WO_3 anodes exhibited photocurrent under illumination at wavelengths ≤640 nm with a faradaic efficiency for O_2 evolution in 1.0 M HClO_4(aq) of nearly unity. Spectroscopic and computational results indicated that deformation of the WO3 host lattice, as well as weak electronic interactions between trapped N_2 and the WO_3 matrix, contributed to the observed red shift in optical absorption. Noble-gas-intercalated WO_3 materials similar to xN_2•WO_3 are predicted to function as photoanodes that are responsive to visible light.
Additional Information
© 2012 American Chemical Society. Received: July 14, 2012. Published: September 28, 2012. We thank Prof. George R. Rossman for discussions and for assistance with the Raman microscope, and Prof. Francois Gygi for discussions of ab initio calculations. This work was supported by the National Science Foundation (NSF) Powering the Planet Center for Chemical Innovation (CCISolar), Grants CHE-0802907 and CHE-0947829. Q.M. was a CCI-Solar Postdoctoral Fellow. P.G.K. thanks the support of the U.S. Department of Energy under the Hydrogen Fuel Initiative. Research was in part carried out in the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology, and in part carried out at Brookhaven National Laboratory under No. DE-AC02-98CH10886 with the U.S. Department of Energy. Use of the Teragrid computational facilities is gratefully acknowledged.Attached Files
Supplemental Material - ja3067622_si_001.pdf
Files
| Name | Size | Download all |
|---|---|---|
|
md5:b40862c67d7e30f8c38367884d9c323d
|
340.1 kB | Preview Download |
Additional details
- Eprint ID
- 36870
- Resolver ID
- CaltechAUTHORS:20130212-095922217
- CHE-0802907
- NSF
- CHE-0947829
- NSF
- NSF Postdoctoral Fellowship
- DE-AC02-98CH10886
- Department of Energy (DOE)
- Created
-
2013-02-23Created from EPrint's datestamp field
- Updated
-
2021-11-09Created from EPrint's last_modified field
- Caltech groups
- CCI Solar Fuels