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

Bangle, Rachel; Sampaio, Renato N.; Troian-Gautier, Ludovic; Meyer, Gerald J.

doi:10.1021/acsami.7b16641

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

Journal Article · Tue Jan 09 00:00:00 EST 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b16641· OSTI ID:1470087

Bangle, Rachel ^[1];

^[1];

^[1]

Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry

The electrografting of [Ru(ttt)(tpy-C₆H_4-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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001011

OSTI ID:: 1470087

Journal Information:: ACS Applied Materials and Interfaces, Vol. 10, 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; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
solar (photovoltaic)
solar (fuels)
photosynthesis (natural and artificial)
hydrogen and fuel cells
electrodes - solar
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materials and chemistry by design
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Title: Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion

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