Quantification strategy of absolute chemiluminescence efficiency for systems of luminol with hydrogen peroxide

Abstract

An important feature to be determined in mechanistic studies on chemiluminescence (CL) is its quantum efficiency, which can give significant chemical reaction information on the influence of the reactant structures and reaction conditions. However, most of the previous quantitative measurements of luminescence and quantum efficiencies are complex and incomplete. To overcome the inconvenience and underestimated quantum efficiency in each measurement, we report a simple and highly effective strategy to determine the absolute CL quantum efficiencies for three systems of luminol with hydrogen peroxide by means of a spectrometer along with an integrating sphere. The integrating sphere facilitated collection of all the emitted light and then transferred it to the spectrometer via an optical fiber proportionally. The CL quantum efficiency was determined by taking the ratio of total photons generated in the reaction system to the number of the limiting reactant molecules consumed. Absolute CL efficiencies of three luminol-H2O2 reaction systems with varied reactant concentrations or coreactants were found to be 37 %, 7.0 % and 6.6 % in a time course, which are much higher than those previously reported values of 1.0–1.3 %. Due to our complete photon collection design, a higher absolute CL efficiency can be realized. Furthermore, spooling CL spectra also provided a powerful visualization tool to observe the real-time CL evolution and devolution, allowing the study on kinetics of CL reaction systems. The above investigations are anticipated to promote further development of CL methodologies and their applications.