Spectroelectrochemical Sensor for Spectroscopically Hard‐to‐detect Metals by in situ Formation of a Luminescent Complex Using Ru(II) as a Model Compound

Lines, Amanda M.; Warner, Joshua D.; Heineman, William R.; Clark, Sue B.; Bryan, Samuel A.

doi:10.1002/elan.201800427

Spectroelectrochemical Sensor for Spectroscopically Hard‐to‐detect Metals by in situ Formation of a Luminescent Complex Using Ru(II) as a Model Compound

Journal Article · Fri Sep 14 04:00:00 EDT 2018 · Electroanalysis

DOI:https://doi.org/10.1002/elan.201800427· OSTI ID:1471128

Lines, Amanda M. ^[1]; Warner, Joshua D. ^[2]; Heineman, William R. ^[3]; Clark, Sue B. ^[1]; Bryan, Samuel A. ^[2]

Energy and Environment Directorate Pacific Northwest National Laboratory Richland WA 99352, Department of Chemistry Washington State University Pullman WA 99163
Energy and Environment Directorate Pacific Northwest National Laboratory Richland WA 99352
Department of Chemistry University of Cincinnati Cincinnati OH 45221

Abstract

Fast, robust, and cost‐effective means of detecting spectroscopically inactive metal species are necessary for field detection and applications within a variety of areas including industry and the nuclear safeguards fields. A sensor based on spectroelectrochemistry is an excellent candidate to meet these needs as it provides improved selectivity for specifically quantifying metal ions by simultaneously monitoring at least two physio‐chemical properties. Ruthenium was chosen as a model system for this study due to its spectroscopic and electrochemical characteristics as well as its relevance within the fuel cycle and industrial fields. Aqueous Ru displays multiple redox couples in which all available oxidation states have poor sensitivity for detection by visible absorption spectroscopy because of the low molar absorptivities. Ru can, however, form complexes with sensitizing ligands such as 2,2′‐bipyridine, where the resulting [Ru(ligand) ₃ ] ²⁺ complex displays a red luminescence with a high quantum yield of emission. This significantly improves detection limits for Ru and allows for the spectroelectrochemical detection of the otherwise hard‐to‐detect metal ion. This work explores the in‐situ generation of Ru(bpy) ₃ complexes in simulated field samples and their subsequent spectroelectrochemical sensing using our sensor methodology.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1471128

Alternate ID(s):: OSTI ID: 1633406

Journal Information:: Electroanalysis, Journal Name: Electroanalysis Journal Issue: 11 Vol. 30; ISSN 1040-0397

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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