High temperature solid-state NMR investigation of reactive carbonate species for catalytic transformations
EMSL Project ID
50644
Abstract
The proposed experiments aim to follow up on preliminary solid-state NMR measurements performed at EMSL to characterize solid base catalysts being investigated for use in a novel hydrocarbon functionalization process. The catalytic materials under observation consist of alkali carbonate salts (M2CO3) dispersed onto high surface area, mesoporous metal oxide supports (e.g. TiO2). Initial measurements confirmed the presence of a chemically distinct, surface-dispersed CO32– species on those catalysts demonstrating the highest activity towards hydrocarbon functionalization. More importantly, measurements at elevated temperature (T = 320°C) provided evidence that the surface CO32– species displays unique structural dynamism at temperatures relevant to the process of interest.The aim of these follow-up measurements is to more thoroughly characterize the dynamic behavior of surface-dispersed CO32– so that this behavior can be unambiguously correlated to catalytic activity. Specifically, we seek to perform variable temperature measurements of the magnetic relaxation properties of 13C nuclei in surface-dispersed M2CO3 catalysts in order to determine the onset temperature at which surface mobility is first observed. This measurement will serve to solidify the link between the structural dynamics and unique reactivity of surface-dispersed CO32– at elevated temperatures.
We are requesting that this proposal be considered for rapid access due to the necessity of these data for submission of a manuscript and a grant proposal to the DOE that describes the carbonate-catalyzed hydrocarbon functionalization process. Our deadline is November 26, 2018 to have a complete dataset for our proposal.
Project Details
Project type
Limited Scope
Start Date
2018-12-12
End Date
2019-02-01
Status
Closed
Released Data Link
Team
Principal Investigator
Related Publications
Xiao D.J., E.D. Chant, A.D. Frankhouser, Y. Chen, A. Yau, N.M. Washton, and M.W. Kanan. 2019. "A closed cycle Esterifying Aromatic Hydrocarbons with CO2 and Alcohol." Nature Chemistry 11, no. 10:940-947. PNNL-SA-144281. doi:10.1038/s41557-019-0313-y