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 · Wed Nov 14 04:00:00 EST 2018 · Electroanalysis

DOI:https://doi.org/10.1002/elan.201800427· OSTI ID:1633406

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

BATTELLE (PACIFIC NW LAB)
UNIVERSITY OF CINCINNATI

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.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1633406

Report Number(s):: PNNL-SA-140865

Journal Information:: Electroanalysis, Journal Name: Electroanalysis Journal Issue: 11 Vol. 30

Country of Publication:: United States

Language:: English

References (53)

Evaluation of tris(4,7-diphenyl-1,10-phenanthrolinedisulfonate)ruthenium(II) as a chemiluminescence reagent McDermott, Geoffrey P.; Zammit, Elizabeth M.; Bowen, Elspeth K. Analytica Chimica Acta, Vol. 634, Issue 2 https://doi.org/10.1016/j.aca.2008.12.030	journal	February 2009
The Determination of the Formulas of Aqueous Ruthenium(III) Species by Means of Ion-exchange Resin: Ru ⁺³ , RuCl ⁺² and RuCl ₂ ⁺ Cady, Howard H.; Connick, Robert E. Journal of the American Chemical Society, Vol. 80, Issue 11 https://doi.org/10.1021/ja01544a012	journal	June 1958
Temperature dependence of the photophysical and photochemical properties of the tris(2,2'-bipyridyl)ruthenium(II) ion in aqueous solution Van Houten, J.; Watts, R. J. Journal of the American Chemical Society, Vol. 98, Issue 16 https://doi.org/10.1021/ja00432a028	journal	August 1976
Trans isomers of ruthenium(II) complexes containing two bipyridine ligands Walsh, Jerry L.; Durham, Bill. Inorganic Chemistry, Vol. 21, Issue 1 https://doi.org/10.1021/ic00131a060	journal	January 1982
Quantum efficiencies of transition-metal complexes. I. d-d Luminescence Crosby, Glenn A.; Demas, James N. Journal of the American Chemical Society, Vol. 92, Issue 25 https://doi.org/10.1021/ja00728a006	journal	December 1970
Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 13. Detection of Aqueous Iron by in Situ Complexation with 2,2‘-Bipyridine Richardson, John N.; Dyer, Aubrey L.; Stegemiller, Michael L. Analytical Chemistry, Vol. 74, Issue 14 https://doi.org/10.1021/ac0111715	journal	July 2002
Hexaaquoruthenium(II) Mercer, E. E.; Buckley, R. R. Inorganic Chemistry, Vol. 4, Issue 12 https://doi.org/10.1021/ic50034a004	journal	December 1965
Simultaneous Detection of Two Analytes Using a Spectroelectrochemical Sensor Andria, Sara E.; Seliskar, Carl J.; Heineman, William R. Analytical Chemistry, Vol. 82, Issue 5 https://doi.org/10.1021/ac902243u	journal	March 2010
Electron Transfer Kinetics of Tris(1,10-phenanthroline)ruthenium(II) Electrooxidation in Aprotic Solvents Winkler, Krzysztof; McKnight, Novelette; Fawcett, W. Ronald The Journal of Physical Chemistry B, Vol. 104, Issue 15 https://doi.org/10.1021/jp993547c	journal	April 2000
Ruthenium(III) chloride in aqueous solution: electrochemical and spectral studies Taqui Khan, M. M.; Ramachandraiah, G.; Rao, A. Prakash Inorganic Chemistry, Vol. 25, Issue 5 https://doi.org/10.1021/ic00225a015	journal	February 1986
Solution mixing and the emission of light in flow-cells for chemiluminescence detection Terry, Jessica M.; Zammit, Elizabeth M.; Slezak, Teo The Analyst, Vol. 136, Issue 5 https://doi.org/10.1039/C0AN00591F	journal	January 2011
Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 11. Design and Evaluation of a Small Portable Sensor for the Determination of Ferrocyanide in Hanford Waste Samples Stegemiller, Michael L.; Heineman, William R.; Seliskar, Carl J. Environmental Science & Technology, Vol. 37, Issue 1 https://doi.org/10.1021/es020601l	journal	January 2003
Time-Resolved Luminescence Spectroelectrochemistry at Screen-Printed Electrodes: Following the Redox-Dependent Fluorescence of [Ru(bpy) ₃ ] ²⁺ Martín-Yerga, Daniel; Pérez-Junquera, Alejandro; Hernández-Santos, David Analytical Chemistry, Vol. 89, Issue 20 https://doi.org/10.1021/acs.analchem.7b01734	journal	September 2017
Multiple state emission from rhodium(I) and iridium(I) complexes Fordyce, W. A.; Rau, H.; Stone, M. L. Chemical Physics Letters, Vol. 77, Issue 2 https://doi.org/10.1016/0009-2614(81)80175-3	journal	January 1981
Charge-transfer luminescence from ruthenium(II) complexes containing tridentate ligands Stone, M. L.; Crosby, G. A. Chemical Physics Letters, Vol. 79, Issue 1 https://doi.org/10.1016/0009-2614(81)85312-2	journal	January 1981
Ruthenium complexes with diazabutadienes. 3. trans and cis Isomers of dichlorobis(diazabutadiene)ruthenium (RN:CR'CR':NR)2RuCl2 Tom Dieck, Heindirk; Kollvitz, Wolfgang; Kleinwaechter, Ingo Inorganic Chemistry, Vol. 23, Issue 17 https://doi.org/10.1021/ic00185a027	journal	August 1984
Chemistry and thermodynamics of ruthenium and some of its inorganic compounds and aqueous species Rard, Joseph A. Chemical Reviews, Vol. 85, Issue 1 https://doi.org/10.1021/cr00065a001	journal	February 1985
Assessing a Spectroelectrochemical Sensor’s Performance for Detecting [Ru(bpy)3]2+ in Natural and Treated Water Abu, Eme A.; Bryan, Samuel A.; Seliskar, Carl J. Electroanalysis, Vol. 24, Issue 7 https://doi.org/10.1002/elan.201200143	journal	June 2012
Charge-transfer excited states of ruthenium(II) complexes. II. Relation of level parameters to molecular structure Hager, G. D.; Watts, R. J.; Crosby, G. A. Journal of the American Chemical Society, Vol. 97, Issue 24 https://doi.org/10.1021/ja00857a014	journal	November 1975
Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes Lines, Amanda M.; Wang, Zheming; Clark, Sue B. Electroanalysis, Vol. 28, Issue 9 https://doi.org/10.1002/elan.201600034	journal	May 2016
The Polarography of Ruthenium (IV) in Perchloric Acid Solutions Niedrach, L. W.; Tevebaugh, A. D. Journal of the American Chemical Society, Vol. 73, Issue 6 https://doi.org/10.1021/ja01150a119	journal	June 1951
Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 20. Detection of Metal Ions in Different Oxidation States Wansapura, Chamika M.; Seliskar, Carl J.; Heineman, William R. Analytical Chemistry, Vol. 79, Issue 15 https://doi.org/10.1021/ac070026+	journal	June 2007
Reaction of chloropentaaquoruthenium(III) with chromium(II). Binuclear intermediates, reduction of perchlorate, and the effect of vanadium(II) Seewald, David; Sutin, Norman; Watkins, Kay O. Journal of the American Chemical Society, Vol. 91, Issue 26 https://doi.org/10.1021/ja01054a019	journal	December 1969
Spectroscopic Studies of Ruthenium(II) Complexes. Assignment of the Luminescence Klassen, D. M.; Crosby, G. A. The Journal of Chemical Physics, Vol. 48, Issue 4 https://doi.org/10.1063/1.1668922	journal	February 1968
Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 2. Demonstration of Selectivity in the Presence of Direct Interferences Shi, Yining; Seliskar, Carl J.; Heineman, William R. Analytical Chemistry, Vol. 69, Issue 23 https://doi.org/10.1021/ac970520l	journal	December 1997
Oxidation of coordinated diamines in bis(2,2'-bipyridine) complexes of ruthenium Brown, Gilbert M.; Weaver, Thomas Ray.; Keene, F. Richard. Inorganic Chemistry, Vol. 15, Issue 1 https://doi.org/10.1021/ic50155a040	journal	January 1976
The Electrode Potential of Ruthenium(IV) and Its Lower Oxidation States Atwood, Donald K.; Vries, Thomas De. Journal of the American Chemical Society, Vol. 84, Issue 14 https://doi.org/10.1021/ja00873a001	journal	July 1962
In Situ Quantification of [Re(CO) ₃ ] ⁺ by Fluorescence Spectroscopy in Simulated Hanford Tank Waste Branch, Shirmir D.; French, Amanda D.; Lines, Amanda M. Environmental Science & Technology, Vol. 52, Issue 3 https://doi.org/10.1021/acs.est.7b04222	journal	January 2018
Luminescence-Based Spectroelectrochemical Sensor for [Tc(dmpe) ₃ ] ^2+/+ (dmpe = 1,2- bis (dimethylphosphino)ethane) within a Charge-Selective Polymer Film Chatterjee, Sayandev; Del Negro, Andrew S.; Edwards, Matthew K. Analytical Chemistry, Vol. 83, Issue 5 https://doi.org/10.1021/ac1030368	journal	March 2011
The Potential of the Ruthenium(II)—Ruthenium(III) Couple ¹ Buckley, R. R.; Mercer, E. E. The Journal of Physical Chemistry, Vol. 70, Issue 10 https://doi.org/10.1021/j100882a014	journal	October 1966
Cis-trans photoisomerization in Ru(bpy)2(OH2)22+. Crystal structure of trans-[Ru(bpy)2(OH2)(OH)](ClO4)2 Durham, Bill; Wilson, Scott R.; Hodgson, Derek J. Journal of the American Chemical Society, Vol. 102, Issue 2 https://doi.org/10.1021/ja00522a026	journal	January 1980
Tris(2,2′-bipyridyl)ruthenium( ii ) chemiluminescence Gorman, Bree A.; Francis, Paul S.; Barnett, Neil W. The Analyst, Vol. 131, Issue 5 https://doi.org/10.1039/B518454A	journal	January 2006
Analytical electrochemistry: methodology and applications of dynamic techniques Heineman, William R.; Kissinger, Peter T. Analytical Chemistry, Vol. 50, Issue 5 https://doi.org/10.1021/ac50028a020	journal	April 1978
Luminescence from Lanthanide(3+) Ions in Solution: Luminescence from Lanthanide(3+) Ions in Solution Døssing, Anders European Journal of Inorganic Chemistry, Vol. 2005, Issue 8 https://doi.org/10.1002/ejic.200401043	journal	March 2005
Electrogenerated chemiluminescence. IX. Electrochemistry and emission from systems containing tris(2,2'-bipyridine)ruthenium(II) dichloride Tokel, Nurhan E.; Bard, Allen J. Journal of the American Chemical Society, Vol. 94, Issue 8 https://doi.org/10.1021/ja00763a056	journal	April 1972
Infra-red Spectra of some Anhydrous Complex Cyanide Acids Jones, D.; Evans, D. F. Nature, Vol. 199, Issue 4890 https://doi.org/10.1038/199277a0	journal	July 1963
Electron-transfer reactions involving the aquoruthenium(II)-aquoruthenium(III) couple Bottcher, Wolfhart; Brown, Gilbert M.; Sutin, Norman Inorganic Chemistry, Vol. 18, Issue 6 https://doi.org/10.1021/ic50196a008	journal	June 1979
Excited states of mixed-ligand chelates of ruthenium(II). Quantum yield and decay time measurements Elfring, W. H.; Crosby, G. A. Journal of the American Chemical Society, Vol. 103, Issue 10 https://doi.org/10.1021/ja00400a032	journal	May 1981
Electrogenerated Chemiluminescence. 59. Rhenium Complexes Richter, Mark M.; Debad, Jeff D.; Striplin, Durwin R. Analytical Chemistry, Vol. 68, Issue 24 https://doi.org/10.1021/ac9606160	journal	January 1996
Spectroscopic characterization of complexes of ruthenium(II) and iridium(III) with 4,4'-diphenyl-2,2'-bipyridine and 4,7-diphenyl-1,10-phenanthroline Crosby, G. A.; Watts, R. J. Journal of the American Chemical Society, Vol. 93, Issue 13 https://doi.org/10.1021/ja00742a016	journal	June 1971
Luminescence from Transition‐Metal Complexes: Tris(2,2′‐bipyridine)‐ and Tris(1,10‐phenanthroline)Ruthenium(II) Crosby, G. A.; Perkins, W. G.; Klassen, D. M. The Journal of Chemical Physics, Vol. 43, Issue 5 https://doi.org/10.1063/1.1696960	journal	September 1965
Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 1. Demonstration of Concept with Ferricyanide Shi, Yining; Slaterbeck, Andrew F.; Seliskar, Carl J. Analytical Chemistry, Vol. 69, Issue 18 https://doi.org/10.1021/ac970322u	journal	September 1997
On the multiplicity of the emitting state of ruthenium(II) complexes Demas, J. N.; Crosby, G. A. Journal of Molecular Spectroscopy, Vol. 26, Issue 1 https://doi.org/10.1016/0022-2852(68)90144-6	journal	May 1968
Bis(2,2′-bipyridine)ruthenium(II) complexes with imidazo[4,5-f ][1,10]-phenanthroline or 2-phenylimidazo[4,5-f ][1,10]phenanthroline Wu, Jian-Zhong; Ye, Bao-Hui; Wang, Lei Journal of the Chemical Society, Dalton Transactions, Issue 8 https://doi.org/10.1039/a605269j	journal	January 1997
An investigation of the mechanism of the Eu(III)/Eu(II) electrode reaction in the presence of edta Kisova, L.; Sluyters-Rehbach, M.; Sluyters, J. H. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 40, Issue 1 https://doi.org/10.1016/S0022-0728(72)80123-2	journal	November 1972
Optical spectrum of hexaaquoruthenium(III) ion and its conjugate base Harzion, Zvi; Navon, Gil Inorganic Chemistry, Vol. 19, Issue 8 https://doi.org/10.1021/ic50210a008	journal	August 1980
Hazards and control of ruthenium in the nuclear fuel cycle Eichholz, Geoffrey G. Progress in Nuclear Energy, Vol. 2, Issue 1 https://doi.org/10.1016/0149-1970(78)90011-2	journal	January 1978
Novel Building Blocks for Biomimetic Assemblies. Synthesis, Characterization, and Spectroscopic and Electrochemical Properties of New Bidentate Ligands Derived from Lysine and Cysteine and Their Complexes with Bis(2,2‘-bipyridine)ruthenium(II) Alsfasser, Ralf; van Eldik, Rudi Inorganic Chemistry, Vol. 35, Issue 3 https://doi.org/10.1021/ic951176i	journal	January 1996
Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2′-bipyridine)ruthenium(ii) complexes Barbante, Gregory J.; Hogan, Conor F.; Wilson, David J. D. The Analyst, Vol. 136, Issue 7 https://doi.org/10.1039/c0an00952k	journal	January 2011
Complexes derived from (RuNO) III and Ru IV Fletcher, John M. Journal of Inorganic and Nuclear Chemistry, Vol. 8 https://doi.org/10.1016/0022-1902(58)80191-8	journal	January 1958
Synthesis, Photo-, and Electrochemistry of Ruthenium Bis(bipyridine) Complexes Comprising a N- heterocyclic Carbene Ligand Leigh, Vivienne; Ghattas, Wadih; Lalrempuia, Ralte Inorganic Chemistry, Vol. 52, Issue 9 https://doi.org/10.1021/ic400347r	journal	April 2013
Spectroelectrochemistry: The combination of optical and electrochemical techniques Heineman, William R. Journal of Chemical Education, Vol. 60, Issue 4 https://doi.org/10.1021/ed060p305	journal	April 1983
Emission Spectroscopy of Ru(bpy) ₂ dppz ²⁺ in Nafion. Probing the Chemical Environment in Cast Films Sabatani, Eyal; Nikol, Hans D.; Gray, Harry B. Journal of the American Chemical Society, Vol. 118, Issue 5 https://doi.org/10.1021/ja9531790	journal	January 1996

Similar Records

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 00:00:00 EDT 2018 · Electroanalysis · OSTI ID:1471128

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

Journal Article · Wed May 04 00:00:00 EDT 2016 · Electroanalysis · OSTI ID:1400558

Electrochemical, spectroscopic, and spectroelectrochemical properties of synthetically useful supramolecular light absorbers with mixed polyazine bridging ligands

Journal Article · Wed Jun 18 00:00:00 EDT 1997 · Inorganic Chemistry · OSTI ID:613728

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

Citation Formats

References (53)

Similar Records

Related Subjects