Thiol-Surface-Engineered Cellulose Nanocrystals in Favor of Copper Ion Uptake.

Cellulose, the most abundant natural polymer on earth, has recently gained attention for a large spectrum of applications. At a nanoscale, nanocelluloses (mainly involving cellulose nanocrystals or cellulose nanofibrils) possess many predominant features, such as highly thermal and mechanical stability, renewability, biodegradability and non-toxicity. More importantly, the surface modification of such nanocelluloses can be efficiently obtained based on the native surface hydroxyl groups, acting as metal ions chelators. Taking into account this fact, in the present work, the sequential process involving chemical hydrolysis of cellulose and autocatalytic esterification using thioglycolic acid was performed to obtain thiol-functionalized cellulose nanocrystals. The change in chemical compositions was attributed to thiol-functionalized groups and explored via the degree of substitution using a back titration method, X-ray powder diffraction, Fourier-transform infrared spectroscopy and thermogravimetric analysis. Cellulose nanocrystals were spherical in shape and ca. 50 nm in diameter as observed via transmission electron microscopy. The adsorption behavior of such a nanomaterial toward divalent copper ions from an aqueous solution was also assessed via isotherm and kinetic studies, elucidating a chemisorption mechanism (ion exchange, metal chelation and electrostatic force) and processing its operational parameters. In contrast to an inactive configure of unmodified cellulose, the maximum adsorption capacity of thiol-functionalized cellulose nanocrystals toward divalent copper ions from an aqueous solution was 4.244 mg g-1 at a pH of 5 and at room temperature.

Cellulose nanocrystals isolated from corn leaf: straightforward immobilization of silver nanoparticles as a reduction catalyst.

As the most abundant natural biopolymer on earth, celluloses have long-term emerged as a capable platform for diverse purposes. In the context of metal nanoparticles applied to catalysis, the alternatives to traditional catalyst supports by using biomass-derived renewable materials, likely nanocelluloses, have been paid a great effort, in spite of being less exploited. In this study, cellulose nanocrystals were isolated from corn leaf via chemical treatment involving alkalizing, bleaching and acid hydrolysis. The crystallinity of obtained cellulose was evaluated in each step, focusing on the effects of reactant concentration and reaction time. Cellulose nanocrystals were characterized by powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), evidencing the presence of cellulose nanospheres (crystallinity index of 67.3% in comparison with 38.4% from untreated raw material) in the size range of 50 nm. Without using any additional surfactants or stabilizers, silver nanoparticles (AgNPs) well-dispersed on the surface of cellulose nanocrystals (silver content of 5.1 wt%) could be obtained by a simple chemical reduction using NaBH4 at room temperature. The catalytic activity was evaluated in the selective reductions of 4-nitrophenol towards 4-aminophenol and methyl orange towards aromatic amine derivatives in water at room temperature. The effects of catalyst amount and reaction time were also studied in both reduction processes, showing near-quantitative conversions within 5 minutes and obeying the pseudo-first-order kinetics, with the apparent kinetic rate constants of 8.9 × 10-3 s-1 (4-nitrophenol) and 13.6 × 10-3 s-1 (methyl orange). The chemical structure of the catalytic system was found to be highly stable during reaction and no metal leaching was detected in reaction medium, evidencing adaptability of cellulose nanocrystals in immobilizing noble metal nanoparticles.

Cycle stability of the electrochemical capacitors patterned with vertically aligned carbon nanotubes in an LiPF6-based electrolyte.

The miniature ultracapacitors, with interdigitated electrodes of vertically aligned carbon nanotubes (VACNTs) and an inter-electrode gap of 20 µm, have been prepared in the LiPF6 organic electrolyte with and without PVdF-HFP gel. PVdF-HFP between two opposing electrodes enhances the device reliability, but lessens its power performance because of the extra diffusion resistance. Also noteworthy are the gel influences on the cycle stability. When the applied voltage is 2.0 or 2.5 V, both the LiPF6 and the gel capacitors exhibit excellent stability, typified by a retention ratio of ≥95% after 10,000 cycles. Their coulombic efficiencies quickly rise up, and hold steady at 100%. Nonetheless, when the applied voltage is 3.5 or 4.0 V, the cycle stability deteriorates, since the negative electrode potential descends below 0.9 V (vs. Li), leading to electrolyte decomposition and SEI formation. For the LiPF6 capacitor, its retention ratio could be around 60% after 10,000 cycles and the coulombic efficiency of 100% is difficult to reach throughout its cycle life. On the other hand, the gel capacitor cycles energy with a much higher retention ratio, >80% after 10,000 cycles, and a better coulombic efficiency, even though electrolyte decomposition still occurs. We attribute the superior stability of the gel capacitor to its extra diffusion resistance which slows down the performance deterioration.