4.6 Article

Physical Strategy to Determine Absolute Electrochemiluminescence Quantum Efficiencies of Coreactant Systems Using a Photon-Counting Photomultiplier Device

Journal

JOURNAL OF PHYSICAL CHEMISTRY C
Volume 125, Issue 40, Pages 22274-22282

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c06342

Keywords

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Funding

  1. Natural Sciences and Engineering Research Council Canada (NSERC) [DG RGPIN-2018-06556, SPG STPGP-2016-493924]
  2. Canada Foundation of Innovation/Ontario Innovation Trust (CFI/OIT) [9040]
  3. University of Western Ontario
  4. Ontario graduate scholarships

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In this study, an absolute method using a photon-counting device was developed to determine the electrochemiluminescence quantum efficiency of coreactant systems. The efficiency of the Ru(bpy)(3)(2+)/ tri-n-propylamine (TPrA) ECL coreactant system was found to be 10.0 +/- 1.1%, showing a 3-fold enhancement compared to annihilation pathways. These findings suggest a promising approach in the expanding field of ECL research.
In this work, using a photon-counting device, we outline our physical strategy to determine absolute electrochemiluminescence (or electrogenerated chemiluminescence, ECL) quantum efficiencies of coreactant systems in comparison with those in annihilation pathways. This absolute method addresses many of the issues with existing relative ECL efficiency measurements, including inconsistencies stemming from nonstandardized experimental conditions and incompatible luminophore systems. The absolute efficiency of the Ru(bpy)(3)(2+)/ tri-n-propylamine (TPrA) ECL coreactant system taken as an example was found to be 10.0 +/- 1.1% for the first time using 10 Hz potential stepping at a TPrA concentration of 10 miM, which quantifies a 3-fold enhancement in efficiency compared to that in the annihilation pathway. Our physical and analytical technique is anticipated to be an immediate and impactful methodology in the expanding field of ECL research.

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