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Ultrafast Lignin Extraction from Unusual Mediterranean Lignocellulosic Residues
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Process-Decoupled Operando Molecular Characterization of Liquid-Phase Lignin Depolymerization by Online

Zhongyue Zhou1, Linyu Zhu1,2, Xintong Xiao1

  • 1School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P.R. China.

Analytical Chemistry
|March 20, 2026
PubMed
Summary

Researchers used a novel reactor and online mass spectrometry to study lignin depolymerization. This method revealed how catalytic hydrogenolysis breaks down complex lignin structures, yielding valuable insights for biomass valorization.

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Area of Science:

  • Chemical Engineering
  • Materials Science
  • Biomass Conversion

Background:

  • Lignin, an abundant biopolymer, is underutilized due to its complex structure.
  • Catalytic depolymerization of lignin is challenging due to structural heterogeneity and limited intermediate accessibility.

Purpose of the Study:

  • To investigate the molecular-level details of alkali Kraft lignin depolymerization.
  • To elucidate structure-reactivity relationships during catalytic depolymerization using advanced analytical techniques.

Main Methods:

  • Utilized a decoupled double-bed flow-through reactor for spatial separation of reactions.
  • Integrated online high-resolution mass spectrometry (HRMS) for real-time product analysis.
  • Employed van Krevelen diagrams and tandem MS for detailed structural elucidation.

Main Results:

  • Online HRMS resolved thousands of molecular species, from monomers to heptamers.
  • Catalytic hydrogenolysis significantly reduced polymer degree and unsaturation.
  • Identified extensive hydrogenation, partial deoxygenation, and cleavage of β-O-4 linkages, with C-C linkages largely preserved.

Conclusions:

  • Online HRMS is a powerful operando tool for studying lignin depolymerization.
  • Flow-through conditions suppress recondensation and promote depolymerization.
  • Provided molecular-level insights for efficient biomass valorization.