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Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water.

ABSTRACT: The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions.

SUBMITTER: Beaumont M

PROVIDER: S-EPMC8097012 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:AbstractThe COVID-19 pandemic outbreak has resulted in the massive fabrication of disposable surgical masks. As the accumulation of discarded face masks represents a booming threat to the environment, here we propose a solution to reuse and upcycle surgical masks according to one of the cornerstones of the circular economy. Specifically, the non-woven cellulosic layer of the masks is used as an environmentally sustainable and highly porous solid support for the controlled deposition of catalytically active metal-oxide nanoparticles. The native cellulosic fibers from the surgical masks are decorated by titanium dioxide (TiO2), iron oxide (FexOy), and cobalt oxide (CoOx) nanoparticles following a simple and scalable approach. The abundant surface -OH groups of cellulose enable the controlled deposition of metal-oxide nanoparticles that are photocatalytically active or shown enzyme-mimetic activities. Importantly, the hydrophilic highly porous character of the cellulosic non-woven offers higher accessibility of the pollutant to the catalytically active surfaces and high retention in its interior. As a result, good catalytic activities with long-term stability and reusability are achieved. Additionally, developed free-standing hybrids avoid undesired media contamination effects originating from the release of nanoscale particles. The upcycling of discarded cellulosic materials, such as the ones of masks, into high-added-value catalytic materials, results an efficient approach to lessen the waste´s hazards of plastics while enhancing their functionality. Interestingly, this procedure can be extended to the upcycling of other systems (cellulosic or not), opening the path to greener manufacturing approaches of catalytic materials.Graphical abstractA novel approach to upcycle discarded cellulosic surgical masks is proposed, providing a solution to reduce the undesired accumulation of discarded face masks originating from the COVID-19 pandemic. The non-woven cellulosic layer formed by fibers is used as solid support for the controlled deposition of catalytically active titanium dioxide (TiO2), iron oxide (FexOy), and cobalt oxide (CoOx) nanoparticles. Cellulosic porous materials are proven useful for the photocatalytic decomposition of organic dyes, while their peroxidase-like activity opens the door to advanced applications such as electrochemical sensors. The upcycling of cellulose nonwoven fabrics into value-added catalytic materials lessens the waste´s hazards of discarded materials while enhancing their functionality.Supplementary informationThe online version contains supplementary material available at 10.1007/s10570-022-04441-9.

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Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water.

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