Methanol-to-Olefins Studied by UV Raman Spectroscopy as Compared to Visible Wavelength: Capitalization on Resonance Enhancement

J Phys Chem Lett. 2024 Jul 4;15(26):6826-6834. doi: 10.1021/acs.jpclett.4c00865. Epub 2024 Jun 25.

Abstract

Resonance Raman spectroscopy can provide insights into complex reaction mechanisms by selectively enhancing the signals of specific molecular species. In this work, we demonstrate that, by changing the excitation wavelength, Raman bands of different intermediates in the methanol-to-hydrocarbons reactions can be identified. We show in particular how UV excitation enhances signals from short-chain olefins and cyclopentadienyl cations during the induction period, while visible excitation better detects later-stage aromatics. However, visible excitation is prone to fluorescence that can obscure Raman signals, and hence, we show how fast fluorescence rejection techniques like Kerr gating are necessary for extracting useful information from visible excitation measurements.