Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO2-Protected Si Photoanodes

Roc Matheu; Ivan A. Moreno-Hernandez; Xavier Sala; Harry B. Gray; Bruce S. Brunschwig; Antoni Llobet; Nathan S. Lewis

doi:10.1021/jacs.7b06800

Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO₂-Protected Si Photoanodes

Roc Matheu, Ivan A. Moreno-Hernandez, Xavier Sala, Harry B. Gray, Bruce S. Brunschwig, Antoni Llobet, Nathan S. Lewis

California Institute of Technology

Research output: Contribution to journal › Article › peer-review

38 Citations (Scopus)

Abstract

A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO₂-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 TiO₂ and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO₂/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 O₂ evolution.

Original language	English
Pages (from-to)	11345-11348
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	33
DOIs	https://doi.org/10.1021/jacs.7b06800
Publication status	Published - Aug 23 2017

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.7b06800

Fingerprint Dive into the research topics of 'Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO<sub>2</sub>-Protected Si Photoanodes'. Together they form a unique fingerprint.

Cite this

Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO₂-Protected Si Photoanodes. / Matheu, Roc; Moreno-Hernandez, Ivan A.; Sala, Xavier; Gray, Harry B.; Brunschwig, Bruce S.; Llobet, Antoni; Lewis, Nathan S.

In: Journal of the American Chemical Society, Vol. 139, No. 33, 23.08.2017, p. 11345-11348.

Research output: Contribution to journal › Article › peer-review

@article{dcf0bb03626046edbe61733114486c5e,

title = "Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO2-Protected Si Photoanodes",

abstract = "A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO2-protected n- or p+-Si coated with multiwalled carbon nanotubes (CNT) and the ruthenium-based water oxidation precatalyst [RuIV(tda)(py-pyr)2(O)], 1(O) (tda2- 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 TiO2 and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO2/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 O2 evolution.",

author = "Roc Matheu and Moreno-Hernandez, {Ivan A.} and Xavier Sala and Gray, {Harry B.} and Brunschwig, {Bruce S.} and Antoni Llobet and Lewis, {Nathan S.}",

note = "Funding Information: 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.",

year = "2017",

month = aug,

day = "23",

doi = "10.1021/jacs.7b06800",

language = "English",

volume = "139",

pages = "11345--11348",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "33",

}

TY - JOUR

T1 - Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO2-Protected Si Photoanodes

AU - Matheu, Roc

AU - Moreno-Hernandez, Ivan A.

AU - Sala, Xavier

AU - Gray, Harry B.

AU - Brunschwig, Bruce S.

AU - Llobet, Antoni

AU - Lewis, Nathan S.

N1 - Funding Information: 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.

PY - 2017/8/23

Y1 - 2017/8/23

N2 - A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO2-protected n- or p+-Si coated with multiwalled carbon nanotubes (CNT) and the ruthenium-based water oxidation precatalyst [RuIV(tda)(py-pyr)2(O)], 1(O) (tda2- 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 TiO2 and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO2/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 O2 evolution.

AB - A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO2-protected n- or p+-Si coated with multiwalled carbon nanotubes (CNT) and the ruthenium-based water oxidation precatalyst [RuIV(tda)(py-pyr)2(O)], 1(O) (tda2- 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 TiO2 and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO2/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 O2 evolution.

UR - http://www.scopus.com/inward/record.url?scp=85028046391&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85028046391&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b06800

DO - 10.1021/jacs.7b06800

M3 - Article

C2 - 28780849

AN - SCOPUS:85028046391

VL - 139

SP - 11345

EP - 11348

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 33

ER -