Campus Units
Chemical and Biological Engineering, Chemistry, Ames Laboratory
Document Type
Article
Publication Version
Submitted Manuscript
Publication Date
7-19-2017
Journal or Book Title
The Journal of Physical Chemistry
Volume
121
Issue
32
First Page
17226
Last Page
17234
DOI
10.1021/acs.jpcc.7b04102
Abstract
High-resolution magic angle spinning (HRMAS) NMR spectroscopy was used to study the effect of mixed solvent systems on the acidity at the solid−liquid interface of solid acid catalysts. A method was developed that can exploit benefits of both solution and solid-state NMR (SSNMR) by wetting porous solids with small volumes of liquids (μL/mg) to create an interfacial liquid that exhibits unique motional dynamics intermediate to an isotropic liquid and a rigid solid. Results from these experiments provide information about the influence of the solvent mixtures on the acidic properties at a solid−liquid interface. Importantly, use of MAS led to spectra with full resolution between water in an acidic environment and that of bulk water. Using mixed solvent systems, the chemical shift of water was used to compare the relative acidity as a function of the hydration level of the DMSO-d6 solvent. Nonlinear increasing acidity was observed as the DMSO-d6 became more anhydrous. 1H HR-MAS NMR experiments on a variety of supported sulfonic acid functionalized materials, suggest that the acid strength and number of acid sites correlates to the degree of broadening of the peaks in the 1H NMR spectra. When the amount of liquid added to the solid is increased (corresponding to a thicker liquid layer), fully resolved water phases were observed. This suggests that the acidic proton was localized predominantly within a 2 nm distance from the solid. EXSY 1H−1H 2D experiments of the thin layers were used to determine the rate of proton exchange for different catalytic materials. These results demonstrated the utility of using (SSNMR) on solid−liquid mixtures to selectively probe catalyst surfaces under realistic reaction conditions for condensed phase systems.
Copyright Owner
American Chemical Society
Copyright Date
2017
Language
en
File Format
application/pdf
Recommended Citation
Johnson, Robert L.; Hanrahan, Michael P.; Mellmer, Max; Dumesic, James A.; Rossini, Aaron J.; and Shanks, Brent H., "The Solvent–Solid Interface of Acid Catalysts Studied by High Resolution MAS NMR" (2017). Chemistry Publications. 993.
https://lib.dr.iastate.edu/chem_pubs/993
Comments
This is manuscript of an article published as Johnson R.L., Hanrahan M.P., Mellmer M., Dumesic J.A., Rossini A.J., Shanks B.H.* The Solvent- Solid Interface of Acid Catalysts Studied by High Resolution MAS NMR, Journal of Physical Chemistry C, 2017, Submitted for Publication.doi: 10.1021/acs.jpcc.7b04102. Posted with permission.