Chemodivergent hydrogenolysis of eucalyptus lignin with Ni@ZIF-8 catalyst

Author(s): Xue Liu ¹ ^, ² ^, ³ ^, ⁴ , Helong Li ¹ ^, ² ^, ³ ^, ⁴ , Ling-Ping Xiao ⁵ ^, ⁶ ^, ⁷ ^, ⁴ , Run-Cang Sun ⁵ ^, ⁶ ^, ⁷ ^, ⁴ , Guoyong Song ¹ ^, ² ^, ³ ^, ⁴

Publication date (Electronic): 2019

Journal: Green Chemistry

Publisher: Royal Society of Chemistry (RSC)

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Abstract

Chemodivergent hydrogenolysis of eucalyptus biomass leading to 4-propanol- or 4-propyl-substituted phenols, together with a well-preserved carbohydrate component, was achieved by using Ni@ZIF-8 catalyst.

Abstract

Reductive catalytic fractionation (RCF) of lignocellulosic biomass, that is depolymerization of the native lignin component into well-defined monomeric phenols in the first step, offers an opportunity to utilize entire biomass components. Herein, we report that Ni@ZIF-8 can serve as a chemodivergent catalyst in RCF of eucalyptus sawdust, thus selectively producing phenolic compounds having either a propyl or propanol end-chain under different reaction conditions. In both cases, high yields of lignin monomers and a high degree of delignification were achieved, next to well-preserved carbohydrate pulp suitable for further processing. A mechanistic study using model compounds indicated that the dehydroxylation at the γ-position of the β- O-4 structure may be involved in the selectivity-controlling step.

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Lignin valorization: improving lignin processing in the biorefinery.

Arthur J Ragauskas, Gregg T Beckham, Mary J Biddy … (2014)

Research and development activities directed toward commercial production of cellulosic ethanol have created the opportunity to dramatically increase the transformation of lignin to value-added products. Here, we highlight recent advances in this lignin valorization effort. Discovery of genetic variants in native populations of bioenergy crops and direct manipulation of biosynthesis pathways have produced lignin feedstocks with favorable properties for recovery and downstream conversion. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for future targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery, and this coupled with genetic engineering will enable new uses for this biopolymer, including low-cost carbon fibers, engineered plastics and thermoplastic elastomers, polymeric foams, fungible fuels, and commodity chemicals.