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1.
ACS Appl Mater Interfaces ; 14(21): 24697-24707, 2022 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-35511115

RESUMEN

Eco-friendly materials with superior thermal insulation and mechanical properties are desirable for improved energy- and space-efficiency in buildings. Cellulose aerogels with structural anisotropy could fulfill these requirements, but complex processing and high energy demand are challenges for scaling up. Here we propose a scalable, nonadditive, top-down fabrication of strong anisotropic aerogels directly from wood with excellent, near isotropic thermal insulation functions. The aerogel was obtained through cell wall dissolution and controlled precipitation in lumen, using an ionic liquid (IL) mixture comprising DMSO and a guanidinium phosphorus-based IL [MTBD][MMP]. The wood aerogel shows a unique structure with lumen filled with nanofibrils network. In situ formation of a cellulosic nanofibril network in the lumen results in specific surface areas up to 280 m2/g and high yield strengths >1.2 MPa. The highly mesoporous structure (average pore diameter ∼20 nm) of freeze-dried wood aerogels leads to low thermal conductivities in both the radial (0.037 W/mK) and axial (0.057 W/mK) directions, showing great potential as scalable thermal insulators. This synthesis route is energy efficient with high nanostructural controllability. The unique nanostructure and rare combination of strength and thermal properties set the material apart from comparable bottom-up aerogels. This nonadditive synthesis approach is believed to contribute significantly toward large-scale design and structure control of biobased aerogels.

2.
Carbohydr Polym ; 274: 118634, 2021 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-34702457

RESUMEN

Combining NaOH with other hydroxide bases with superior dissolution properties can be a means of improving dissolution of cellulose. However, this raises questions about how the size and structure of cellulose vary when dissolved in different hydroxide bases. Here, cellulose in aqueous solutions of NaOH, Tetramethylammonium hydroxide (TMAH), Benzyltrimethylammonium hydroxide (Triton B) and previously studied equimolar solutions of NaOH/TMAH and NaOH/Triton B were investigated using small angle X-ray scattering, static and dynamic light scattering. The results show that cellulose in NaOH(aq) is largely aggregated and that the more hydrophobic TMAH and Triton are capable of molecularly dissolving cellulose into worm-like conformations, stiffer than in NaOH. The dissolution properties of mixtures are highly dependent on the compatibility of the individual bases; in line with previous observations of the properties of the solutions which now could be correlated to the structure of the cellulose on a nano- and microscale.

3.
ACS Appl Mater Interfaces ; 13(18): 21724-21732, 2021 May 12.
Artículo en Inglés | MEDLINE | ID: mdl-33909392

RESUMEN

Hydrogen (H2) sensors that can be produced en masse with cost-effective manufacturing tools are critical for enabling safety in the emerging hydrogen economy. The use of melt-processed nanocomposites in this context would allow the combination of the advantages of plasmonic hydrogen detection with polymer technology; an approach which is held back by the slow diffusion of H2 through the polymer matrix. Here, we show that the use of an amorphous fluorinated polymer, compounded with colloidal Pd nanoparticles prepared by highly scalable continuous flow synthesis, results in nanocomposites that display a high H2 diffusion coefficient in the order of 10-5 cm2 s-1. As a result, plasmonic optical hydrogen detection with melt-pressed fluorinated polymer nanocomposites is no longer limited by the diffusion of the H2 analyte to the Pd nanoparticle transducer elements, despite a thickness of up to 100 µm, thereby enabling response times as short as 2.5 s at 100 mbar (≡10 vol. %) H2. Evidently, plasmonic sensors with a fast response time can be fabricated with thick, melt-processed nanocomposites, which paves the way for a new generation of robust H2 sensors.

4.
Carbohydr Polym ; 252: 117105, 2021 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-33183584

RESUMEN

Periodate oxidation of polysaccharides has transitioned from structural analysis into a modification method for engineered materials. This review summarizes the research on this topic. Fibers, fibrils, crystals, and molecules originating from forests that have been subjected to periodate oxidation can be crosslinked with other entities via the generated aldehyde functionality, that can also be oxidized or reduced to carboxyl or alcohol functionality or used as a starting point for further modification. Periodate-oxidized materials can be subjected to thermal transitions that differ from the native cellulose. Oxidation of polysaccharides originating from forests often features oxidation of structures rather than liberated molecules. This leads to changes in macro, micro, and supramolecular assemblies and consequently to alterations in physical properties. This review focuses on these aspects of the modulation of structural hierarchies due to periodate oxidation.

5.
J Colloid Interface Sci ; 437: 283-290, 2015 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-25441362

RESUMEN

The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability.

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