Monitoring Molecular Weight Changes during Technical Lignin Depolymerization by Operando Attenuated Total Reflectance Infrared Spectroscopy and Chemometrics

Khaled N.M. Khalili; Peter de Peinder; Jacqueline Donkers; Richard J.A. Gosselink; Pieter C.A. Bruijnincx; Bert M. Weckhuysen

doi:10.1002/cssc.202101853

Monitoring Molecular Weight Changes during Technical Lignin Depolymerization by Operando Attenuated Total Reflectance Infrared Spectroscopy and Chemometrics

Khaled N.M. Khalili
, Peter de Peinder
, Jacqueline Donkers
, Richard J.A. Gosselink
, Pieter C.A. Bruijnincx^*
, Bert M. Weckhuysen

^*Corresponding author for this work

Sub Organic Chemistry and Catalysis

Wageningen University & Research

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Technical lignins are increasingly available at industrial scale, offering opportunities for valorization, such as by (partial) depolymerization. Any downstream lignin application requires careful tailoring of structural properties, such as molecular weight or functional group density, properties that are difficult to control or predict given the structure variability and recalcitrance of technical lignins. Online insight into changes in molecular weight (M_w), to gauge the extent of lignin depolymerization and repolymerization, would be highly desired to improve such control, but cannot be readily provided by the standard ex-situ techniques, such as size exclusion chromatography (SEC). Herein, operando attenuated total reflectance infrared (ATR-IR) spectroscopy combined with chemometrics provided temporal changes in M_w during lignin depolymerization with high resolution. More specifically, ex-situ SEC-derived M_w and polydispersity data of kraft lignin subjected to aqueous phase reforming conditions could be well correlated with ATR-IR spectra of the reaction mixture as a function of time. The developed method showed excellent regression results and relative error, comparable to the standard SEC method. The method developed has the potential to be translated to other lignin depolymerization processes.

Original language	English
Pages (from-to)	5517-5524
Number of pages	8
Journal	ChemSusChem
Volume	14
Issue number	24
Early online date	23 Nov 2021
DOIs	https://doi.org/10.1002/cssc.202101853
Publication status	Published - 17 Dec 2021

Bibliographical note

Funding Information:
This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7- PEOPLE-2013-ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan-European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged.

Funding Information:
This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7‐ PEOPLE‐2013‐ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan‐European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged.

Publisher Copyright:
© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH

Funding

This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7‐ PEOPLE‐2013‐ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan‐European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged.

Keywords

ATR-IR spectroscopy
chemometrics
lignin valorization
operando spectroscopy
size exclusion chromatography

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ChemSusChem - 2021 - Khalili - Monitoring Molecular Weight Changes during Technical Lignin Depolymerization by OperandoFinal published version, 2.17 MBLicence: CC BY

Cite this

@article{a0fb5c2840e4409abad6ffbea908d3e0,

title = "Monitoring Molecular Weight Changes during Technical Lignin Depolymerization by Operando Attenuated Total Reflectance Infrared Spectroscopy and Chemometrics",

abstract = "Technical lignins are increasingly available at industrial scale, offering opportunities for valorization, such as by (partial) depolymerization. Any downstream lignin application requires careful tailoring of structural properties, such as molecular weight or functional group density, properties that are difficult to control or predict given the structure variability and recalcitrance of technical lignins. Online insight into changes in molecular weight (Mw), to gauge the extent of lignin depolymerization and repolymerization, would be highly desired to improve such control, but cannot be readily provided by the standard ex-situ techniques, such as size exclusion chromatography (SEC). Herein, operando attenuated total reflectance infrared (ATR-IR) spectroscopy combined with chemometrics provided temporal changes in Mw during lignin depolymerization with high resolution. More specifically, ex-situ SEC-derived Mw and polydispersity data of kraft lignin subjected to aqueous phase reforming conditions could be well correlated with ATR-IR spectra of the reaction mixture as a function of time. The developed method showed excellent regression results and relative error, comparable to the standard SEC method. The method developed has the potential to be translated to other lignin depolymerization processes.",

keywords = "ATR-IR spectroscopy, chemometrics, lignin valorization, operando spectroscopy, size exclusion chromatography",

author = "Khalili, \{Khaled N.M.\} and \{de Peinder\}, Peter and Jacqueline Donkers and Gosselink, \{Richard J.A.\} and Bruijnincx, \{Pieter C.A.\} and Weckhuysen, \{Bert M.\}",

note = "Funding Information: This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7- PEOPLE-2013-ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan-European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged. Funding Information: This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7‐ PEOPLE‐2013‐ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan‐European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged. Publisher Copyright: {\textcopyright} 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH",

year = "2021",

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doi = "10.1002/cssc.202101853",

language = "English",

volume = "14",

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AU - Khalili, Khaled N.M.

AU - de Peinder, Peter

AU - Donkers, Jacqueline

AU - Gosselink, Richard J.A.

AU - Bruijnincx, Pieter C.A.

AU - Weckhuysen, Bert M.

N1 - Funding Information: This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7- PEOPLE-2013-ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan-European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged. Funding Information: This work has been performed within the framework of the SUBicat program. The authors gratefully acknowledge the financial support from the European Commission (SuBiCat Initial Training Network, Call FP7‐ PEOPLE‐2013‐ITN, grant no. 607044). The contribution of COST Action LignoCOST (CA17128 Pan‐European network on sustainable lignin valorisation) supported by COST (European Cooperation in Science and Technology), in promoting interaction, exchange of knowledge and collaborations in the field of lignin valorisation is gratefully acknowledged. Publisher Copyright: © 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH

PY - 2021/12/17

Y1 - 2021/12/17

N2 - Technical lignins are increasingly available at industrial scale, offering opportunities for valorization, such as by (partial) depolymerization. Any downstream lignin application requires careful tailoring of structural properties, such as molecular weight or functional group density, properties that are difficult to control or predict given the structure variability and recalcitrance of technical lignins. Online insight into changes in molecular weight (Mw), to gauge the extent of lignin depolymerization and repolymerization, would be highly desired to improve such control, but cannot be readily provided by the standard ex-situ techniques, such as size exclusion chromatography (SEC). Herein, operando attenuated total reflectance infrared (ATR-IR) spectroscopy combined with chemometrics provided temporal changes in Mw during lignin depolymerization with high resolution. More specifically, ex-situ SEC-derived Mw and polydispersity data of kraft lignin subjected to aqueous phase reforming conditions could be well correlated with ATR-IR spectra of the reaction mixture as a function of time. The developed method showed excellent regression results and relative error, comparable to the standard SEC method. The method developed has the potential to be translated to other lignin depolymerization processes.

AB - Technical lignins are increasingly available at industrial scale, offering opportunities for valorization, such as by (partial) depolymerization. Any downstream lignin application requires careful tailoring of structural properties, such as molecular weight or functional group density, properties that are difficult to control or predict given the structure variability and recalcitrance of technical lignins. Online insight into changes in molecular weight (Mw), to gauge the extent of lignin depolymerization and repolymerization, would be highly desired to improve such control, but cannot be readily provided by the standard ex-situ techniques, such as size exclusion chromatography (SEC). Herein, operando attenuated total reflectance infrared (ATR-IR) spectroscopy combined with chemometrics provided temporal changes in Mw during lignin depolymerization with high resolution. More specifically, ex-situ SEC-derived Mw and polydispersity data of kraft lignin subjected to aqueous phase reforming conditions could be well correlated with ATR-IR spectra of the reaction mixture as a function of time. The developed method showed excellent regression results and relative error, comparable to the standard SEC method. The method developed has the potential to be translated to other lignin depolymerization processes.

KW - ATR-IR spectroscopy

KW - chemometrics

KW - lignin valorization

KW - operando spectroscopy

KW - size exclusion chromatography

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DO - 10.1002/cssc.202101853

M3 - Article

AN - SCOPUS:85119663070

SN - 1864-5631

VL - 14

SP - 5517

EP - 5524

JO - ChemSusChem

JF - ChemSusChem

IS - 24

ER -

Monitoring Molecular Weight Changes during Technical Lignin Depolymerization by Operando Attenuated Total Reflectance Infrared Spectroscopy and Chemometrics

Abstract

Bibliographical note

Funding

Keywords

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