Enhanced Hydrogen Generation through Low-Temperature Plasma Treatment of Waste Aluminum for Hydrolysis Reaction.

This study investigates the low-temperature hydrogen plasma treatment approach for the improvement of hydrogen generation through waste aluminum (Al) reactions with water and electricity generation via proton-exchange membrane fuel cell (PEM FC). Waste Al scraps were subjected to ball milling and treated using two different low-temperature plasma regimes: Diode and magnetron-initiated plasma treatment. Hydrolysis experiments were conducted using powders with different treatments, varying molarities, and reaction temperatures to assess hydrogen generation, reaction kinetics, and activation energy. The results indicate that magnetron-initiated plasma treatment significantly enhances the hydrolysis reaction kinetics compared to untreated powders or those treated with diode-generated plasma. Analysis of chemical bonds revealed that magnetron-initiated hydrogen plasma treatment takes advantage by promoting a dual procedure: Surface cleaning and Al nanocluster deposition on top of Al powders. Moreover, it was modeled that such H2 plasma could penetrate up to 150 Å depth. Meanwhile, electricity generation tests demonstrate that only 0.2 g of treated Al powder can generate approximately 1 V for over 300 s under a constant 2.5 Ω load and 1.5 V for 2700 s with a spinning fan.

A Study of Parallel and Competitive Reaction Schemes in Kinetic Modeling of Plastic Pyrolysis.

Pyrolysis is a technology capable of harnessing energy from challenging-to-recycle plastics, thus mitigating the necessity for incineration or landfill disposal. To optimize the plastic pyrolysis process, reliable models for product yield prediction are imperative. This study endeavors to determine the suitability of lumped models, a widely used approach for modeling biomass and coal pyrolysis, in accurately estimating product yields in the context of plastic pyrolysis. To address this question, three lumped models with parallel and competitive reaction mechanisms were compared and fitted to experimental data collected across a broad temperature range. The aim is to identify which models can elucidate the most appropriate reaction pathway for the plastic pyrolysis process. The first model in this study assesses whether the commonly employed wood pyrolysis kinetic models can effectively fit the experimental data from plastic pyrolysis. Subsequently, the final two models introduce additional reactions into the pyrolysis process, prompting the authors to investigate the necessity of these supplementary reaction pathways for accurately predicting plastic pyrolysis outcomes. This investigation seeks to pinpoint the essential terms and discern which ones may be safely omitted from the models. The results of the study reveal that the model incorporating secondary tar reactions with gas, tar, and char is the most precise in predicting the products of plastic pyrolysis, surpassing all other combinations evaluated in this research.

Dataset of biomass characteristics and net output power from downdraft biomass gasifier integrated power production unit.

This dataset includes 1032 runs from a biomass downdraft gasifier integrated with power production unit that is fed by 86 different types of biomasses from different groups (e.g. wood and woody biomasses, herbaceous and agricultural biomasses, animal biomasses, mixed biomasses and contaminated biomasses) and under various operating conditions. The dataset covers elemental and proximate analysis of various biomasses, operation conditions and the net output power from the biomass gasification-power production (BG-PP) in each case/run. This article has been submitted via another Elsevier journal as a co-submission, titled "Artificial neural network integrated with thermodynamic equilibrium modeling of downdraft biomass gasification-power production plant" [1]. In fact, this dataset has been used to train and test the developed Artificial neural network modeling of a downdraft BG-PP in our original research paper [1].

Titanium Dioxide Nanotubes as Model Systems for Electrosorption Studies.

Highly ordered titanium dioxide nanotubes (TiO2 NTs) were fabricated through anodization and tested for their applicability as model electrodes in electrosorption studies. The crystalline structure of the TiO2 NTs was changed without modifying the nanostructure of the surface. Electrosorption capacity, charging rate, and electrochemical active surface area of TiO2 NTs with two different crystalline structures, anatase and amorphous, were investigated via chronoamperometry, cyclic voltammetry, and electrochemical impedance spectroscopy. The highest electrosorption capacities and charging rates were obtained for the anatase TiO2 NTs, largely because anatase TiO2 has a reported higher electrical conductivity and a crystalline structure that can potentially accommodate small ions within. Both electrosorption capacity and charging rate for the ions studied in this work follow the order of Cs⁺ > Na⁺ > Li⁺, regardless of the crystalline structure of the TiO2 NTs. This order reflects the increasing size of the hydrated ion radii of these monovalent ions. Additionally, larger effective electrochemical active surface areas are required for larger ions and lower conductivities. These findings point towards the fact that smaller hydrated-ions experience less steric hindrance and a larger comparative electrostatic force, enabling them to be more effectively electrosorbed.

Reversible oxygen scavenging at room temperature using electrochemically reduced titanium oxide nanotubes.

A material capable of rapid, reversible molecular oxygen uptake at room temperature is desirable for gas separation and sensing, for technologies that require oxygen storage and oxygen splitting such as fuel cells (solid-oxide fuel cells in particular) and for catalytic applications that require reduced oxygen species (such as removal of organic pollutants in water and oil-spill remediation). To date, however, the lowest reported temperature for a reversible oxygen uptake material is in the range of 200-300 °C, achieved in the transition metal oxides SrCoOx (ref. 1) and LuFe2O(4+x) (ref. 2) via thermal cycling. Here, we report rapid and reversible oxygen scavenging by Ti(2-x) nanotubes at room temperature. The uptake and release of oxygen is accomplished by an electrochemical rather than a standard thermal approach. We measure an oxygen uptake rate as high as 14 mmol O2 g(-1) min(-1), ∼2,400 times greater than commercial, irreversible oxygen scavengers. Such a fast oxygen uptake at a remarkably low temperature suggests a non-typical mechanistic pathway for the re-oxidation of Ti(2-x). Modelling the diffusion of oxygen, we show that a likely pathway involves 'exceptionally mobile' interstitial oxygen produced by the oxygen adsorption and decomposition dynamics, recently observed on the surface of anatase.

Ultrafast carrier dynamics in nanostructures for solar fuels.

Sunlight can be used to drive chemical reactions to produce fuels that store energy in chemical bonds. These fuels, such as hydrogen from splitting water, have much larger energy density than do electrical storage devices. The efficient conversion of clean, sustainable solar energy using photoelectrochemical and photocatalytic systems requires precise control over the thermodynamics, kinetics, and structural aspects of materials and molecules. Generation, thermalization, trapping, interfacial transfer, and recombination of photoexcited charge carriers often occur on femtosecond to picosecond timescales. These short timescales limit the transport of photoexcited carriers to nanometer-scale distances, but nanostructures with high surface-to-volume ratios can enable both significant light absorption and high quantum efficiency. This review highlights the importance of understanding ultrafast carrier dynamics for the generation of solar fuels, including case studies on colloidal nanostructures, nanostructured photoelectrodes, and photoelectrodes sensitized with molecular chromophores and catalysts.

Synthesis of nanomaterials using self-assembled nanotemplates.

Nanoporous alumina templates and titania nanotube arrays have emerged as highly important materials due to their many potential applications in a variety of research areas. The templates are prepared using an electrochemical anodization process starting from metallic Al or Ti films. Several different synthesis routes for the deposition of such templates have been demonstrated in literature. This article provides an overview of the various synthesis routes that may be employed. The templates have diverse applications and may also be utilized in the electrodeposition of nanowire arrays of a variety of materials, such as metals, semiconductors, etc. A brief overview of these deposition methods is also provided.

Exciton-like trap states limit electron mobility in TiO2 nanotubes.

Nanoparticle films have become a promising low-cost, high-surface-area electrode material for solar cells and solar fuel production. Compared to sintered nanoparticle films, oriented polycrystalline titania nanotubes offer the advantage of directed electron transport, and are expected to have higher electron mobility. However, macroscopic measurements have revealed their electron mobility to be as low as that of nanoparticle films. Here, we show, through time-resolved terahertz spectroscopy, that low mobility in polycrystalline TiO(2) nanotubes is not due to scattering from grain boundaries or disorder-induced localization as in other nanomaterials, but instead results from a single sharp resonance arising from exciton-like trap states. If the number of these states can be lowered, this could lead to improved electron transport in titania nanotubes and significantly better solar cell performance.

Synergistic effect between anatase and rutile TiO2 nanoparticles in dye-sensitized solar cells.

A synergistic effect between anatase and rutile TiO2 is known, in which the addition of rutile can remarkably enhance the photocatalytic activity of anatase in the degradation of organic contaminants. In this study, mixed-phase TiO2 nanocomposites consisting of anatase and rutile nanoparticles (NPs) were prepared for use as photoanodes in dye-sensitized solar cells (DSSCs) and were characterized by using UV-vis spectroscopy, powder X-ray diffraction and scanning electron microscopy. The addition of 10-15% rutile significantly improved light harvesting and the overall solar conversion efficiency of anatase NPs in DSSCs. The underlying mechanism for the synergistic effect in DSSCs is now explored by using time-resolved terahertz spectroscopy. It is clearly demonstrated that photo-excited electrons injected into the rutile NPs can migrate to the conduction band of anatase NPs, enhancing the photocurrent and efficiency. Interfacial electron transfer from rutile to anatase, similar to that in heterogeneous photocatalysis, is proposed to account for the synergistic effect in DSSCs. Our results further suggest that the synergistic effect can be used to explain the beneficial effect of TiCl4 treatment on DSSC efficiency.

High-aspect ratio nano-noodles of alumina and titania.

We report the formation of high-aspect ratio rod-like structures or 'nano-noodles' of alumina or titania. Such structures are formed either by rapid anodization of aluminum/titanium foil or by long-term post-anodization treatment of porous templates. Specifically, the nano-noodle structures form during anodization in highly acidic electrolytes and/or at high anodization voltages, or when porous templates are etched for long periods of time in an acid. Growth mechanism for such structures is also proposed.