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Title: Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion

Abstract

The electrografting of [Ru(ttt)(tpy-C 6H 4-N 2 +)] 3+, where “ttt” is 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine, was investigated on several wide band gap metal oxide surfaces (TiO 2, SnO 2, ZrO 2, ZnO, In 2O 3:Sn) and compared to structurally analogous sensitizers that differed only by the anchoring group, i.e., -PO 3H 2 and -COOH. An optimized procedure for diazonium electrografting to semiconductor metal oxides is presented that allowed surface coverages that ranged between 4.7 × 10 -8 and 10.6 × 10 -8 mol cm -2 depending on the nature of the metal oxide. FTIR analysis showed the disappearance of the diazonium stretch at 2266 cm -1 after electrografting. XPS analysis revealed a characteristic peak of Ru 3d at 285 eV as well as a peak at 531.6 eV that was attributed to O 1s in Ti-O-C bonds. Photocurrents were measured to assess electron injection efficiency of these modified surfaces. The electrografted sensitizers exhibited excellent stability across a range of pHs spanning from 1 to 14, where classical binding groups such as carboxylic and phosphonic derivatives were hydrolyzed.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470087
Grant/Contract Number:  
SC0001011
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Related Information: UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar; charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Bangle, Rachel, Sampaio, Renato N., Troian-Gautier, Ludovic, and Meyer, Gerald J. Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion. United States: N. p., 2018. Web. doi:10.1021/acsami.7b16641.
Bangle, Rachel, Sampaio, Renato N., Troian-Gautier, Ludovic, & Meyer, Gerald J. Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion. United States. doi:10.1021/acsami.7b16641.
Bangle, Rachel, Sampaio, Renato N., Troian-Gautier, Ludovic, and Meyer, Gerald J. Tue . "Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion". United States. doi:10.1021/acsami.7b16641. https://www.osti.gov/servlets/purl/1470087.
@article{osti_1470087,
title = {Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion},
author = {Bangle, Rachel and Sampaio, Renato N. and Troian-Gautier, Ludovic and Meyer, Gerald J.},
abstractNote = {The electrografting of [Ru(ttt)(tpy-C6H4-N2+)]3+, where “ttt” is 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine, was investigated on several wide band gap metal oxide surfaces (TiO2, SnO2, ZrO2, ZnO, In2O3:Sn) and compared to structurally analogous sensitizers that differed only by the anchoring group, i.e., -PO3H2 and -COOH. An optimized procedure for diazonium electrografting to semiconductor metal oxides is presented that allowed surface coverages that ranged between 4.7 × 10-8 and 10.6 × 10-8 mol cm-2 depending on the nature of the metal oxide. FTIR analysis showed the disappearance of the diazonium stretch at 2266 cm-1 after electrografting. XPS analysis revealed a characteristic peak of Ru 3d at 285 eV as well as a peak at 531.6 eV that was attributed to O 1s in Ti-O-C bonds. Photocurrents were measured to assess electron injection efficiency of these modified surfaces. The electrografted sensitizers exhibited excellent stability across a range of pHs spanning from 1 to 14, where classical binding groups such as carboxylic and phosphonic derivatives were hydrolyzed.},
doi = {10.1021/acsami.7b16641},
journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 3,
volume = 10,
place = {United States},
year = {2018},
month = {1}
}

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