Mechanistic Study of Diaryl Ether Bond Cleavage during Palladium‐Catalyzed Lignin Hydrogenolysis

Li, Yanding; Karlen, Steven D.; Demir, Benginur; Kim, Hoon; Luterbacher, Jeremy; Dumesic, James A.; Stahl, Shannon S.; Ralph, John

doi:10.1002/cssc.202000753

Mechanistic Study of Diaryl Ether Bond Cleavage during Palladium‐Catalyzed Lignin Hydrogenolysis

Journal Article · Mon Apr 20 00:00:00 EDT 2020 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.202000753· OSTI ID:1615442

^[1]; ^[2]; ^[3]; Kim, Hoon ^[2]; ^[4]; ^[3]; ^[5]; ^[6]

Department of Biological Systems Engineering University of Wisconsin-Madison Madison WI 53706 USA, DOE Great Lakes Bioenergy Research Center Madison WI 53726 USA, Department of Chemical Engineering Massachusetts Institute of Technology Cambridge MA 02142 USA
DOE Great Lakes Bioenergy Research Center Madison WI 53726 USA, Department of Biochemistry University of Wisconsin-Madison Madison WI 53706 USA
DOE Great Lakes Bioenergy Research Center Madison WI 53726 USA, Department of Chemical and Biological Engineering University of Wisconsin-Madison Madison WI 53706 USA
Institute of Chemical Sciences and Engineering École Polytechnique Fédérale de Lausanne Route Cantonale 1015 Lausanne Switzerland
DOE Great Lakes Bioenergy Research Center Madison WI 53726 USA, Department of Chemistry University of Wisconsin-Madison Madison WI 53706 USA
Department of Biological Systems Engineering University of Wisconsin-Madison Madison WI 53706 USA, DOE Great Lakes Bioenergy Research Center Madison WI 53726 USA, Department of Biochemistry University of Wisconsin-Madison Madison WI 53706 USA

Abstract

Hydrogenolysis has emerged as one of the most effective means of converting polymeric lignin into monoaromatic fragments of value. Reported yields may be higher than for other methods and can exceed the theoretical yields estimated from measures of the content of lignin's most readily cleaved alkyl‐aryl ether bonds in β‐ether units. The high yields suggest that other units in lignin are being cleaved. Diaryl ether units are important units in lignin, and their cleavage has been examined previously using simple model compounds, such as diphenyl ether. Herein, the hydrogenolysis of model compounds that closely resemble the native lignin 4‐O‐5 diaryl ether units was analyzed. The results provided unexpected insights into the reactivity and partial cleavage of these compounds. The models and lignin polymer produced not only monomers, but also unusual 1,3,5‐ meta ‐substituted aromatics that appear to be diagnostic for the presence and the cleavage of the 4‐O‐5 diaryl ether unit in lignin.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018409

OSTI ID:: 1615442

Alternate ID(s):: OSTI ID: 1803391

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 17 Vol. 13; ISSN 1864-5631

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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