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Topics in Catalysis

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03-06-2023 | Original Paper

Insights into Acetic Acid Binding and Ketene Formation on Anatase TiO₂(101)

Authors: Christopher R. O’Connor, Runze Ma, Gregory Collinge, Mal-Soon Lee, Greg A. Kimmel, Zdenek Dohnálek

Published in: Topics in Catalysis | Issue 15-16/2023

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Abstract

Understanding the adsorption and reactivity of carboxylic acids on oxide surfaces is of great interest in catalysis for biomass upgrading via ketonization, a carbon–carbon coupling reaction. Herein, we investigate the adsorption and reaction of acetic acid on anatase TiO₂(101) using scanning tunneling microscopy, infrared spectroscopy, temperature programmed reaction, and density functional theory calculations. We demonstrate the adsorption of acetic acid can form two intermediates: (1) dissociated, bidentate acetate with an associated bridging hydroxyl, and (2) molecular, monodentate acetic acid. The coexistence of ordered phases with increasing monolayer (ML) saturation coverages consisting of (1) pure acetate (0.5 ML), (2) mixed acetate/acetic acid (0.67 ML), (3) mixed acetate/acetic acid (1.0 ML) and (4) pure acetic acid demonstrates similar energetics for both acetate and acetic acid species. Under ultra-high vacuum conditions, the presence of both monodentate acetic acid and bidentate acetate was observed below room temperature, while solely bidentate acetate was observed up to 575 K. The deprotonation of acetic acid produces water at 280 K, while the thermal decomposition of bidentate acetate produces ketene and acetic acid at 645 K. This model study provides detailed insight into the stability and reactivity of carboxylic acid surface-bound intermediates, which could participate during ketonization reactions for biomass upgrading.

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Title: Insights into Acetic Acid Binding and Ketene Formation on Anatase TiO2(101)
Authors: Christopher R. O’Connor
Runze Ma
Gregory Collinge
Mal-Soon Lee
Greg A. Kimmel
Zdenek Dohnálek
Publication date: 03-06-2023
Publisher: Springer US
Published in: Topics in Catalysis / Issue 15-16/2023
Print ISSN: 1022-5528
Electronic ISSN: 1572-9028
DOI: https://doi.org/10.1007/s11244-023-01828-1

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