Crystallization Pathways and Evolution of Morphologies and Structural Defects of α-MnO2 under Air Annealing.

Manganese dioxide nanomaterials have wide applications in many areas from catalysis and Li-ion batteries to gas sensing. Understanding the crystallization pathways, morphologies, and formation of defects in their structure is particularly important but still a challenging issue. Herein, we employed an arsenal of X-ray diffraction (XRD), scanning electron microscopy (SEM), neutron diffraction, positron annihilation spectroscopies, and ab initio calculations to investigate the evolution of the morphology and structure of α-MnO2 nanomaterials prepared via reduction of KMnO4 solution with C2H5OH prior to being annealed in air at 200-600 °C. We explored a novel evolution that α-MnO2 nucleation can be formed even at room temperature and gradually developed to α-MnO2 nanorods at above 500 °C. We also found the existence of H+ or K+ ions in the [1 × 1] tunnels of α-MnO2 and observed the simultaneous presence of Mn and O vacancies in α-MnO2 crystals at low temperatures. Increasing the temperature removed these O vacancies, leaving only the Mn vacancies in the samples.

Cellulose nanocrystals extracted from rice husk using the formic/peroxyformic acid process: isolation and structural characterization.

Cellulose derived from biomass is a renewable resource with numerous applications. Using formic/peroxyformic acid at atmospheric pressure, cellulose nanocrystals (CNC) were isolated from rice husk (RH) in this study. This method was an excellent way to get rid of lignin and hemicelluloses from RH. The cellulose was subsequently acid hydrolyzed by H2SO4 (64%) for 30 minutes at 45 °C. The chemical and microstructure analysis showed that the lignin and hemicellulose contents of raw RH had been eliminated, and the crystallinity content of CNC was 67.16%. According to transmission electron microscopy (TEM) morphological analysis, CNC measured 19 ± 3.3 nm in diameter, 195 ± 24 nm in length, and 10.2 ± 6.8 in aspect ratio. The thermal stability of RH and CNC was also investigated using thermogravimetric analysis (TGA). These encouraging findings demonstrated the potential for reusing RH agricultural waste to create CNC and include nanocomposites as a reinforcing material.