This paper presents the limitations and potential of ATR-FTIR spectroscopy applied to the study of cellulosic textile collections. The technique helps to differentiate natural fibres according to the content of lignin, pectin, hemicellulose, and wax, although some problematic issues should be considered. The spectral differences derived from the environmental humidity uptake and the plant composition are reviewed and discussed in the light of new experimental data. Diagnostic bands are proposed that can discriminate between different fibres from different plants. The contribution of ageing is also considered, demonstrating that sometimes aged fibres cannot be reliably recognised. In contrast, the potential of ATR-FTIR spectroscopy to discriminate between natural and modified fibres is discussed and proven. The best results were obtained when microinvasive ATR-FTIR spectroscopy was coupled with SEM observations. The proposed protocol was tested on microsamples of various cellulosic materials from traditional Japanese samurai armours dating from the 16th to the 20th centuries (Morigi Collection, Museo delle Culture, Lugano, Switzerland). The results facilitated a complete characterisation of the materials and demonstrated that the protocol can be used to study a wide variety of cellulosic materials, including both natural and man-modified fibres, and paper.
Biochar nanoparticles (BC NPs), produced by low temperature pyrolysis (350 °C) of microalgae (Nannochloropsis sp.) and nutshells, are proposed as low-cost and sustainable co-catalysts to promote the photocatalytic activity of TiO2 nanotube (NT) arrays towards the degradation of methylene blue (MB) used as an organic pollutant model molecule. BC NPs (size < 25 nm) were obtained by treating bulk BC (i.e., biomass after pyrolysis) by sonication–centrifugation cycles in a water solution. The filtered BC NPs dispersion was deposited by simple drop-casting on the TiO2 NT support. The BC loading was varied by performing multiple depositions. Photocatalytic experiments under UV light (365 nm) revealed that the decoration with BC NPs significantly improves the TiO2 photoactivity. Such enhancement is mainly influenced by the amount of BC deposited; upon optimizing the BC deposition conditions, the rate of photocatalytic degradation of MB increases approximately three times with respect to bare TiO2, almost irrespective of the nature of the raw material. The greater photocatalytic activity of BC-TiO2 can be attributed to the synergistic combination of reactant/product adsorption and catalytic degradation of the adsorbed organic pollutant, as well as an improved charge carrier separation and electron transfer.
Ocean sediments consist mainly of calcium carbonate and organic matter (phytoplankton debris). Once subducted, some carbon is removed from the slab and returns to the atmosphere as CO2 in arc magmas. Its isotopic signature is thought to reflect the bulk fraction of inorganic (carbonate) and organic (graphitic) carbon in the sedimentary source. Here we challenge this assumption by experimentally investigating model sediments composed of 13C-CaCO3 + 12C-graphite interacting with water at pressure, temperature and redox conditions of an average slab–mantle interface beneath arcs. We show that oxidative dissolution of graphite is the main process controlling the production of CO2, and its isotopic composition reflects the CO2/CaCO3 rather than the bulk graphite/CaCO3 (i.e., organic/inorganic carbon) fraction. We provide a mathematical model to relate the arc CO2 isotopic signature with the fluid–rock ratios and the redox state in force in its subarc source.
Pt nanoparticles are typically decorated as co‐catalyst on semiconductors to enhance the photocatalytic performance. Due to the low abundance and high cost of Pt, reaching a high activity with minimized co‐catalyst loadings is a key challenge in the field. We explore a dewetting‐dealloying strategy to fabricate on TiO2 nanotubes nanoporous Pt nanoparticles, aiming at improving the co‐catalyst mass activity for H2 generation. For this, we sputter first Pt‐Ni bi‐layers of controllable thickness (nm range) on highly ordered TiO2 nanotube arrays, and then induce dewetting‐alloying of the Pt‐Ni bi‐layers by a suitable annealing step in a reducing atmosphere: the thermal treatment causes the Pt and Ni films to agglomerate and at the same time mix with each other, forming on the TiO2 nanotube surface metal islands of a mixed PtNi composition. In a subsequent step we perform chemical dealloying of Ni that is selectively etched out from the bimetallic dewetted islands, leaving behind nanoporous Pt decorations. Under optimized conditions, the nanoporous Pt‐decorated TiO2 structures show a>6 times higher photocatalytic H2 generation activity compared to structures modified with a comparable loading of dewetted, non‐porous Pt. We ascribe this beneficial effect to the nanoporous nature of the dealloyed Pt co‐catalyst, which provides an increased surface‐to‐volume ratio and thus a more efficient electron transfer and a higher density of active sites at the co‐catalyst surface for H2 evolution.