Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO_2-Protected Si Photoanodes
Abstract
A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO_2-protected n- or p+-Si coated with multiwalled carbon nanotubes (CNT) and the ruthenium-based water oxidation precatalyst [Ru^(IV)(tda)(py-pyr)_2(O)], 1(O) (tda^(2–) is [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylato and py-pir is 4-(pyren-1-yl)-N-(pyridin-4-ylmethyl)butanamide). The Ru complex was immobilized by π–π stacking onto CNTs that had been deposited by drop casting onto Si electrodes coated with 60 nm of amorphous TiO_2 and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO_2/C/CNT/[1+1(O)] electrodes exhibited current densities of 1 mA cm^(–2) at 1.07 V vs NHE. The current density was maintained for >200 min at a constant potential while intermittently collecting voltammograms that indicated that over half of the Ru was still in molecular form after O_2 evolution.
Additional Information
© 2017 American Chemical Society. Received: June 30, 2017; Published: August 7, 2017. The National Science Foundation under NSF Center CHE-1305124 provided support for H.B.G., I.M.H., N.S.L., B.S.B., and R.M. and for supplies at Caltech, I.M.H. was supported by a NSF Graduate Research Fellowship (Grant No. DGE-1144469). Instrumentation support was also provided by the Molecular Materials Resource Center of the Beckman Institute at California Institute of Technology. R.M., A.L., and X.S. acknowledge MINECO and FEDER (CTQ2016-80058-R, CTQ2015-64261-R, SEV 2013-0319, ENE2016-82025-REDT, CTQ2016-81923-REDC), AGAUR (2014-SGR-915), and "La Caixa" foundation. We acknowledge Dr. K. Sun for helpful discussions. The authors declare no competing financial interest.Attached Files
Supplemental Material - ja7b06800_si_001.pdf
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Additional details
- Eprint ID
- 80464
- DOI
- 10.1021/jacs.7b06800
- Resolver ID
- CaltechAUTHORS:20170816-083201966
- NSF
- CHE-1305124
- NSF Graduate Research Fellowship
- DGE-1144469
- Ministerio de Economía y Competitividad (MINECO)
- CTQ2016-80058-R
- Ministerio de Economía y Competitividad (MINECO)
- CTQ2015-64261-R
- Ministerio de Economía y Competitividad (MINECO)
- SEV 2013-0319
- Ministerio de Economía y Competitividad (MINECO)
- ENE2016-82025-REDT
- Ministerio de Economía y Competitividad (MINECO)
- CTQ2016-81923-REDC
- Agència de Gestió d'Ajuts Universitaris i de Recerca
- 2014-SGR-915
- La Caixa Foundation
- Created
-
2017-08-16Created from EPrint's datestamp field
- Updated
-
2021-11-15Created from EPrint's last_modified field
- Caltech groups
- Kavli Nanoscience Institute