In situ Detection of Cobaloxime Intermediates During Photocatalysis Using Hollow-Core Photonic Crystal Fiber Microreactors |
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| Authors: | Dr Takashi Lawson Dr Alexander S Gentleman Jonathan Pinnell Dr Annika Eisenschmidt Dr Daniel Antón-García Dr Michael H Frosz Prof Erwin Reisner Dr Tijmen G Euser |
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| Institution: | 1. NanoPhotonics Centre, Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE UK;2. Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK;3. Max Planck Institute for the Science of Light, Staudtstr. 2, 91058 Erlangen, Germany |
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| Abstract: | Hollow-core photonic crystal fibers (HC-PCFs) provide a novel approach for in situ UV/Vis spectroscopy with enhanced detection sensitivity. Here, we demonstrate that longer optical path lengths than afforded by conventional cuvette-based UV/Vis spectroscopy can be used to detect and identify the CoI and CoII states in hydrogen-evolving cobaloxime catalysts, with spectral identification aided by comparison with DFT-simulated spectra. Our findings show that there are two types of signals observed for these molecular catalysts; a transient signal and a steady-state signal, with the former being assigned to the CoI state and the latter being assigned to the CoII state. These observations lend support to a unimolecular pathway, rather than a bimolecular pathway, for hydrogen evolution. This study highlights the utility of fiber-based microreactors for understanding these and a much wider range of homogeneous photocatalytic systems in the future. |
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| Keywords: | Cobaloximes Hollow-Core Photonic Crystal Fibers Laser Spectroscopy Optofluidics Photocatalysis |
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