Degradation and Crystallization of Cellulose in Hydrogen Chloride Vapor for High‐Yield Isolation of Cellulose Nanocrystals

Kontturi, Eero; Meriluoto, Anne; Penttilä, Paavo A.; Baccile, Niki; Malho, Jani Markus; Potthast, Antje; Rosenau, Thomas; Ruokolainen, Janne; Serimaa, Ritva; Laine, Janne; Sixta, Herbert

doi:10.1002/anie.201606626

Cited by 129 publications

(159 citation statements)

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“…In conventional LODP studies, scission plots of acid hydrolyzed cellulose I and II typically follow the shape of asymptotic exponential curves, with cellulose II degraded at a faster rate. [25,[32][33][34] Curiously, the enzymatic degradation patterns of cellulose polymorphs also follow this trend. [35][36][37][38] Here, however, the kinetic scission plots of cellulose II and III II exhibit trends which have not, to our knowledge, previously been reported in the literature.…”

Section: Resultsmentioning

confidence: 90%

“…Glucose is formed on the course of hydrolysis, but it stays in the cellulose matrix unless washed out with water afterward. [25] Obviously, a direct analogy between pressure and time isotherms cannot be made and so an adsorption model was developed through an interpolation. Due to the lack of a mechanistic model for the time dependence of HCl adsorption, appropriate functions were fit to the experimental adsorption data to develop the adsorption model.…”

Section: Resultsmentioning

confidence: 99%

“…Native cellulose I (from cotton linters) was included as a reference; however, its hydrolysis is discussed in detail in our previous work. [25] We stress here that all the studied cellulose grades are semicrystalline and hydrolysis occurs mainly in the disordered segments of the cellulose microfibrils. Polymorphism presents just one aspect of the degradation behavior and therefore, a rigorous treatise on the kinetics of degradation and, importantly, HCl vapor adsorption has been included.…”

mentioning

confidence: 92%

“…a subtle growth in the degree of crystallinity. [25] Moreover, the effect of the solvent can be neglected with this approach. In addition to the conceptual demonstration, the fundamental data presented here for three artificial (nonnative) cellulose polymorphs facilitates the potential use of cellulosic materials for functionalities that are based on the utilization of a reactive gas or vapor on a substrate.…”

mentioning

confidence: 99%

“…In fact, the recycling of the liquid acid is generally considered the bottleneck in the acidcatalyzed hydrolysis of cellulose. [26] Because the degradation of native cellulose I was already extensively investigated in our previous work, [25] the substrates used in this study were cellulose II (regenerated viscose via the dissolution of cellulose I), and cellulose III I and III II produced through an ethylenediamine treatment and subsequent rinsing by methanol of cellulose I and II, respectively ( Figure 1). Cellulose II possesses an altered hydrogen bonding pattern and different chain alignment to cellulose I. Cellulose I crystals possess parallel alignment between conjugate chains whereas the chain alignment in cellulose II is antiparallel.…”

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confidence: 99%

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The Effect of Polymorphism on the Kinetics of Adsorption and Degradation: A Case of Hydrogen Chloride Vapor on Cellulose

Niinivaara

Arshath

Nieminen

et al. 2018

Advanced Sustainable Systems

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crystalline arrangements. With natural as well as synthetic polymers, research on polymorphism has generally focused on the formation and characterization of different polymorphs, and not on their specific reactivity, [1][2][3] whereas different polymorphs of inorganic molecules have been shown to play a key role in, for example, the catalytic performance of metal oxides. [4][5][6][7][8] Artificial tuning of the crystalline form for specific functionalities is a potent, yet underexplored tool in contemporary polymer science. This is all the more pronounced in the case of natural polymers. Here, we demonstrate the aforementioned concept by presenting how the kinetics of a simple cellulose degradation reaction is distinctly influenced by the cellulose polymorph.Most crystalline polymers are polymorphic in nature and the crystalline form noticeably influences both their physical and the chemical properties, such as melting point, conductivity, accessibility, or susceptibility to chemical reactions. [9][10][11] Cellulose, the natural polysaccharide responsible for the structural scaffold of all plants cells, is no different. The native crystalline order of cellulose, as dictated by biosynthesis, [12] can be deliberately modified with specific treatments, [13][14][15] leading to substantial alterations in the material behavior.Here, the degradation of three artificially prepared cellulose polymorphs during acid catalyzed hydrolysis (Figure 1) is explored. Chemical degradation of cellulose is a topical issue for two principal reasons: obtaining cellulosic nanomaterials for novel renewable applications [16][17][18] as well as deriving small molecular substances, namely commodity chemicals or sugars that are subsequently used for fermentation for biofuel production. [19,20] Cellulose hydrolysis is nearly always studied in a heterogeneous solid/liquid system. [14] By contrast, this study focuses on the degradation of different cellulose polymorphs in a solid/gas system, namely a solid cellulose substrate in an acidic hydrogen chloride vapor atmosphere. The distinctive gas and vapor sorption behavior of all cellulosic materials is a characteristic feature which strongly depends on, among other factors, their crystallinity and crystalline form. [14,[21][22][23][24] Acid hydrolysis is one of the most investigated reactions on native cellulose. Regardless, our recent work on the HCl vapor hydrolysis of native cellulose (cellulose I) exposed many peculiarities in comparison to the conventional solid/liquid setup, such as Control of the reactivity of natural polymers -such as semicrystalline cellulosethrough polymorphic transitions is a potent, yet underexplored tool in modern polymer science. Here, the degradation behavior of three artificial cellulose polymorphs (cellulose II, III I , and III II ) in the presence of hydrogen chloride vapor is explored. While the ultimate results of hydrolyses correspond to those found for aqueous HCl, the kinetic scission models exhibit a unique trend for each polymorph, unlike those reported...

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