In situ Detection of Cobaloxime Intermediates During Photocatalysis Using Hollow-Core Photonic Crystal Fiber Microreactors.

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 Co^I and Co^II 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 Co^I state and the latter being assigned to the Co^II 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.

SUBMITTER: Lawson T 

PROVIDER: S-EPMC10946874 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature