Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis

Zeyou Pan, Allen Puente-Urbina, Syeda Rabia Batool, Andras Bodi, Xiangkun Wu, Zihao Zhang, Jeroen A. Bokhoven () and Patrick Hemberger ()
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Zeyou Pan: Paul Scherrer Institute
Allen Puente-Urbina: ETH Zurich
Syeda Rabia Batool: ETH Zurich
Andras Bodi: Paul Scherrer Institute
Xiangkun Wu: Paul Scherrer Institute
Zihao Zhang: Paul Scherrer Institute
Jeroen A. Bokhoven: Paul Scherrer Institute
Patrick Hemberger: Paul Scherrer Institute

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract Unveiling catalytic mechanisms at a molecular level aids rational catalyst design and selectivity control for process optimization. In this study, we find that the Brønsted acid site density of the zeolite catalyst efficiently controls the guaiacol catalytic pyrolysis mechanism. Guaiacol demethylation to catechol initiates the reaction, as evidenced by the detected methyl radicals. The mechanism branches to form either fulvenone (c-C5H4 = C = O), a reactive ketene intermediate, by catechol dehydration, or phenol by acid-catalyzed dehydroxylation. At high Brønsted acid site density, fulvenone formation is inhibited due to surface coordination configuration of its precursor, catechol. By quantifying reactive intermediates and products utilizing operando photoelectron photoion coincidence spectroscopy, we find evidence that ketene suppression is responsible for the fivefold phenol selectivity increase. Complementary fulvenone reaction pathway calculations, along with 29Si NMR-MAS spectroscopy results corroborate the mechanism. The proposed, flexible operando approach is applicable to a broad variety of heterogeneous catalytic reactions.

Date: 2023
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DOI: 10.1038/s41467-023-40179-z

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