Supported molybdenum oxides for the aldol condensation reaction of acetaldehyde

Rasmussen, Mathew J.; Najmi, Sean; Innocenti, Giada; Medford, Andrew J.; Sievers, Carsten; Medlin, J. Will

doi:10.1016/j.jcat.2022.03.002

Supported molybdenum oxides for the aldol condensation reaction of acetaldehyde

Journal Article · Tue Mar 08 00:00:00 EST 2022 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2022.03.002· OSTI ID:1981655

Rasmussen, Mathew J. ^[1]; ^[2]; Innocenti, Giada ^[2]; Medford, Andrew J. ^[2]; Sievers, Carsten ^[2]; Medlin, J. Will ^[1]

Univ. of Colorado, Boulder, CO (United States)
Georgia Institute of Technology, Atlanta, GA (United States)

The (retro-)aldol condensation reaction is an important chemical transformation in the upgrading of biomass-derived compounds into fuels and valuable specialty chemicals. In this study, we found that supported molybdenum oxide (MoO_x) catalysts were active and selective for the aldol condensation of acetaldehyde to crotonaldehyde under steady-state reactor conditions. Through a combination of transmission electron microscopy (TEM), ultraviolet–visible (UV–VIS) diffuse reflectance spectroscopy, Fourier transform infrared (FTIR) spectroscopy of adsorbed pyridine, and steady-state reactor testing, we determined that highly dispersed MoO_x has a strong interaction with a γ-Al₂O₃ support resulting in optimal catalyst performance at low weight loadings. In contrast, MoO_x particles supported on SiO₂ have a weaker interaction with the support, resulting in a monotonic relationship between Mo loading and aldol condensation activity. The Lewis acid site density and strength are important parameters for predicting aldol condensation activity across all samples. The concentration of weak acid sites had a poor correlation with aldol condensation activity, most likely because these sites are too weak to activate acetaldehyde for the reaction. Medium and strong acid sites both had good correlations to aldol condensation activity. Results from X-ray absorption near edge structure (XANES) and acetaldehyde temperature programmed desorption (TPD) indicated that partially reduced MoO_x was more active for aldol condensation, but pretreatment in reducing or oxidizing environments had no significant effect on steady-state catalytic activity. Finally, characterization of spent catalyst samples through temperature programmed oxidation (TPO) and thermogravimetric analysis (TGA) revealed that catalysts with high densities of strong acid sites tended to form more carbonaceous deposits on the surface over the course of the reaction.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1981655

Alternate ID(s):: OSTI ID: 1860526

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 408; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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