Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Li, Ning; Bian, Huiyang; Zhu, J. Y.; Ciesielski, Peter N.; Pan, Xuejun

doi:10.1039/D1GC00145K

Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Journal Article · Tue Mar 16 04:00:00 EDT 2021 · Green Chemistry

DOI:https://doi.org/10.1039/D1GC00145K· OSTI ID:1781611

Li, Ning; Bian, Huiyang; Zhu, J. Y.; ; Pan, Xuejun

Preparing cellulose II nanocrystals (CNC II) requires a polymorph transformation of natural cellulose I feedstocks. The transformation is usually achieved via a process such as mercerization or dissolution–regeneration. This study demonstrated a new method to prepare CNC II directly from bleached kraft pulp (BKP, a commercially available cellulose I feedstock) in a mildly acidic lithium bromide trihydrate (MALBTH) system, a concentrated (~61 wt%) solution of LiBr in water with a very low concentration (2.5 mM) of sulfuric acid. First, the BKP was treated in the MALBTH system to generate a cellulose II hydrolysis solid residue (CHR) with a yield of 64–86%, during which the selective hydrolysis of disordered cellulose and the polymorph transformation were completed simultaneously. Then, subsequent oxidation of the CHR by ammonium persulfate (APS, 0.1–0.6 M) resulted in the CNC II with high yield (up to 62%), high crystallinity (over 90%), rich surface carboxyl group (0.3–1.2 mmol g-1 cellulose), excellent colloidal stability (up to -59 mV zeta potential), and high thermal stability. The CNC II had a tunable length (26–57 nm), determined by the conditions of the MALBTH hydrolysis and the APS oxidation, but similar lateral dimension (8–10 nm). The characterization of the CHR by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy verified the polymorphic transformation from cellulose I to II during the MALBTH treatment. The swelling of the BKP in the MALBTH enabled cellulose crystallites to slide and reassemble, which completed the rearrangement of cellulose chains from parallel to anti-parallel conformation (polymorph transformation from cellulose I to II). This study provided an efficient and green method to produce cellulose II nanocrystals with controllable aspect ratios via the simultaneous hydrolysis and polymorph transformation of cellulose I feedstocks.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1781611

Report Number(s):: NREL/JA-2800-79131; MainId:33357; UUID:f6fafe8b-5ef0-4961-a381-2f5d4b45beac; MainAdminID:19788

Journal Information:: Green Chemistry, Journal Name: Green Chemistry Journal Issue: 7 Vol. 23

Country of Publication:: United States

Language:: English

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Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

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