Metal ion and hydrogen bonding synergistically mediated carboxylated lignin/cellulose nanofibrils composite film

Dan Luo; Gaofeng Sun; Yilin Wang; Xuan Shu; Jie Chen; Mengya Sun; Xiuyu Liu; Chao Liu; Huining Xiao; Tingting Xu; Hongqi Dai; Xuelian Zhou; Chen Huang; Huiyang Bian

doi:10.1016/j.carbpol.2023.121456

Metal ion and hydrogen bonding synergistically mediated carboxylated lignin/cellulose nanofibrils composite film

Carbohydr Polym. 2024 Jan 1:323:121456. doi: 10.1016/j.carbpol.2023.121456. Epub 2023 Oct 4.

Authors

Dan Luo¹, Gaofeng Sun¹, Yilin Wang¹, Xuan Shu¹, Jie Chen¹, Mengya Sun¹, Xiuyu Liu², Chao Liu¹, Huining Xiao³, Tingting Xu¹, Hongqi Dai¹, Xuelian Zhou⁴, Chen Huang⁵, Huiyang Bian⁶

Affiliations

¹ Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, China.
² Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Minzu University, Nanning 530006, China.
³ Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada.
⁴ Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Jiangsu Province Key Laboratory of Biomass Energy and Materials, Nanjing 210042, China.
⁵ Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Jiangsu Province Key Laboratory of Biomass Energy and Materials, Nanjing 210042, China. Electronic address: huangchen3127@njfu.edu.cn.
⁶ Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, China; Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Minzu University, Nanning 530006, China. Electronic address: hybian1992@njfu.edu.cn.

PMID: 37940315
DOI: 10.1016/j.carbpol.2023.121456

Abstract

In order to alleviate the resource and environmental problems caused by plastic film materials, the development of biodegradable cellulose-based films is crucial. Inspired by the strengthening mechanism of cellulose-lignin network from wood, carboxylated lignin (CL) was isolated using maleic acid (MA) pretreatment catalyzed by metal chlorides. Compared with pure MA, the presence of metal ions yielded CL with high carboxyl content (0.34 mmol/g), small size and good dispersibility. CL was then composited with CNF to prepare various CL/cellulose nanofibrils (CNF) composite films. When the addition of ferric chloride was 0.3 mmol/g maleic acid, the corresponding composite films exhibited highest tensile strength (180.0 MPa), Young's modulus (13.0 GPa) and excellent ultraviolet blocking rate (97.0 %). Meanwhile, the interaction forces measured by atomic force microscope showed that the binding between CNF and various CLs (276-406 nN) was higher than that between pure CNFs (202 nN), verifying that CL enhanced the mechanical properties of composite films. In summary, this work constructs a super-strong network between CL and CNF synergistically mediated by metal ion crosslinking and hydrogen bonding, which can be a promising alternative to replace conventional plastics in multiple areas.

Keywords: Carboxylated lignin nanoparticles; Cellulose nanofibrils; Composite film; Hydrogen bonding; Metal ion cross-linking.