A Spectroscopic Paradox: The Interaction of Methanol with ZSM-5 at Room Temperature

• DOI: 10.1007/s11244-021-01462-9
• Publication Date: 2021-07-29T19:08:41Z
• Authors: Andrea Zachariou; Alexander P. Hawkins; Russell F. Howe; Nathan Barrow; Jonathan Bradley; Paul Collier; David Lennon; Stewart F. Parker
• Keywords: EP/R026939/1; Supplementary Data; General Chemistry; 02 engineering and technology; QD Chemistry; 540; NMR; Catalysis; Inelastic neutron scattering (INS); HZSM-5; APH (EP/P510506/1; Room temperature methoxylation; Engineering and Physical Sciences Research Council (EPSRC); EP/R026815/1; DRIFTS; AZ (EP/N509176/1; QD; 0210 nano-technology; Hydrogen bonded methanol

AbstractThe adsorption of methanol in HZSM-5 at low temperatures has long been regarded as an associative process involving hydrogen bonding to the acidic zeolite hydroxyl groups. Recent studies employing inelastic neutron scattering spectroscopy (INS) have reported that complete dissociation to methoxylate the zeolite occurs at 298 K, and infrared evidence for a partial dissociation at 298 K has also been described. Here we investigate the apparent contradictions between different techniques, using a combination of INS, infrared spectroscopy and solid-state NMR spectroscopy, including isotopic substitution experiments. Different possible explanations are proposed and considered; we conclude that at room temperature methanol is very largely associatively adsorbed, although the presence of some small extent (>1%) of methoxylation cannot be ruled out.