Recent Advances in Conjugated Polymers for Visible-Light-Driven Water Splitting

With the ambition of solving the challenges of the shortage of fossil fuels and their associated environmental pollution, visible-light-driven splitting of water into hydrogen and oxygen using semiconductor photocatalysts has emerged as a promising technology to provide environmentally friendly energy vectors. Among the current library of developed photocatalysts, organic conjugated polymers present unique advantages of sufficient light-absorption efficiency, excellent stability, tunable electronic properties, and economic applicability. As a class of rising photocatalysts, organic conjugated polymers offer high flexibility in tuning the framework of the backbone and porosity to fulfill the requirements for photocatalytic applications. In the past decade, significant progress has been made in visible-light-driven water splitting employing organic conjugated polymers. The recent development of the structural design principles of organic conjugated polymers (including linear, crosslinked, and supramolecular self-assembled polymers) toward efficient photocatalytic hydrogen evolution, oxygen evolution, and overall water splitting is described, thus providing a comprehensive reference for the field. Finally, current challenges and perspectives are also discussed.     

Reactive Oxygen and Nitrogen Species in Defense/Stress Responses Activated by Chitosan in Sycamore Cultured Cells

Chitosan (CHT) is a non-toxic and inexpensive compound obtained by deacetylation of chitin, the main component of the exoskeleton of arthropods as well as of the cell walls of many fungi. In agriculture CHT is used to control numerous diseases on various horticultural commodities but, although different mechanisms have been proposed, the exact mode of action of CHT is still unknown. In sycamore (Acer pseudoplatanus L.) cultured cells, CHT induces a set of defense/stress responses that includes production of H₂O₂ and nitric oxide (NO). We investigated the possible signaling role of these reactive molecules in some CHT-induced responses by means of inhibitors of production and/or scavengers. The results show that both reactive nitrogen and oxygen species are not only a mere symptom of stress conditions but are involved in the responses induced by CHT in sycamore cells. In particular, NO appears to be involved in a cell death form induced by CHT that shows apoptotic features like DNA fragmentation, increase in caspase-3-like activity and release of cytochrome c from the mitochondrion. On the contrary, reactive oxygen species (ROS) appear involved in a cell death form induced by CHT that does not show these apoptotic features but presents increase in lipid peroxidation.     

Triphenylphosphonium (TPP)-Based Antioxidants: A New Perspective on Antioxidant Design

Mitochondrial oxidative damage and dysfunction contribute to a wide range of human diseases. Considering the limitation of conventional antioxidants and that mitochondria are the main source of reactive oxygen species (ROS) which induce oxidative damage, mitochondria-targeted antioxidants which can selectively block mitochondrial oxidative damage and prevent various types of cell death have been widely developed. As a lipophilic cation, triphenylphosphonium (TPP) has been commonly used in designing mitochondria-targeted antioxidants. Conjugated with the TPP moiety, antioxidants can achieve more than 1000-fold higher mitochondrial concentration depending on cell membrane potentials and mitochondrial membrane potentials. Herein we discuss the deficiencies of conventional antioxidants and the advantages of mitochondrial targeting, and review various types of TPP-based mitochondria-targeted antioxidants. These provide theoretical and background support for the design of new anti-oxidant.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.     

Performance of surface ionic conduction single chamber fuel cell prepared by the sol gel method

The performance of surface ionic conduction single chamber fuel cell (SIC‐SCFC) prepared by the sol gel method was studied on electric characteristics due to the differences of the operating temperature and humidity, the electrode distance and electrolyte film depth, and multiple cells with the series and parallel connections. The SIC–SCFC was arranged the both anode of Pt and cathode of Au on the boehmite electrolyte. The open circuit voltage (OCV) of single cell achieved a maximum of 530mV in the dry gas mixtures of O₂/H₂=50% in room temperature operation, and but it became decrease as over 60%. The OCV was maintained the constant value between operating temperatures of 30°C to 80°C, and but it was decreased sharply at over 90°C because a humidity on the cell became lower as increasing operating temperature. Then, the cell property was improved to 120°C by adding to the humidity of 70% using a humidifier. The electrode distance and the electrolyte film depth of SIC‐SCFC found to be contributed to the reductions of the cell resistance and the surface roughness on the electrode, respectively. Moreover, the power property of SIC‐SCFC was significantly improved by cell stacks comprised of the series or parallel connection of a cell.     

Rapid synthesis of garnet-type Li7La3Zr2O12 solid electrolyte with superior electrochemical performance

Li₇La₃Zr₂O₁₂-based garnet-type solid electrolytes are promising candidates for use in all-solid-state lithium batteries (ASSLBs). However, their potential in large-scale commercial applications is largely hindered by the time/energy-consuming and lithium-wasting synthetic method which typically needs a long-duration high temperature solid state reaction process. Herein we invent a fast preparation route that involves a short-period thermal reaction (1100 °C for 10 min) in laboratory muffle furnaces following by conventional hot pressing technique to get almost fully dense (Al, Ga, Ta, Nb)-doped garnet-type electrolytes with high phase purity (>99.9 %). The large and compact grains, low porosity and high phase purities of garnet ceramic electrolytes synthesized in this study ensure superior electrochemical performance. Particularly, Ga-doped cubic Li₇La₃Zr₂O₁₂ shows extremely low E_a values (0.17?0.18 eV) and record-high lithium ionic conductivities (>2 × 10^?3 S cm^-1 at 25 °C).     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Fabrication of BSCF-based mixed ionic-electronic conducting membrane by electrophoretic deposition for oxygen separation application

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF), which exhibits a high mixed oxide ionic-electronic conduction, was used for the fabrication of an oxygen separation membrane. An asymmetric structure, which was a thin and dense BSCF membrane layer supported on a porous BSCF substrate, was fabricated by the electrophoretic deposition method (EPD). Porous BSCF supports were prepared by the uniaxial pressing method using a powder mixture with BSCF and starch as the pore-forming agent (0–50 wt.%). The sintering behaviors of the porous support and the thin layer were separately characterized by dilatometry to determine the co-fired temperature at which cracking did not occur. A crack-free and thin dense membrane layer, which had about a 15 μm thickness and >95% relative density, was obtained after optimizing the processes of EPD and sintering. The dense/porous interface was well-bonded and the oxygen permeation flux was 2.5 ml (STP) min⁻¹ cm^-2 at 850 °C.     

Impact of non‐solvent on regeneration of cellulose dissolved in 1‐(carboxymethyl)pyridinium chloride ionic liquid

Cellulose dissolved in ionic liquid (1‐(carboxymethyl)pyridinium chloride)/water (60/40 w/w) mixture is regenerated in various non‐solvents, namely water, ethanol, methanol and acetone, to gain more insight into the contribution of non‐solvent medium to the morphology of regenerated cellulose. To this end, the initial and regenerated celluloses were characterized with respect to crystallinity, thermal stability, chemical structure and surface morphology using wide‐angle X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. According to the results, regardless of non‐solvent type, all regenerated samples have the same chemical structure and lower crystallinity in comparison to the initial cellulose, making them a promising candidate for efficient biofuel production based on enzymatic hydrolysis of cellulose. The reduction in crystallinity of regenerated samples is explained based on the potential of the non‐solvent to break the hydrogen bonds between cellulose chains and ionic liquid molecules as well as the affinity of water and non‐solvent which can be evaluated based on Hansen solubility parameter. The latter also determines the phase‐separation mechanism during the regeneration process, which in turn affects surface morphology of the regenerated cellulose. The pivotal effect of regenerated cellulose crystallinity on its thermal stability is also demonstrated. Regenerated cellulose with lower crystallinity is more susceptible to molecular rearrangement during heating and hence exhibits enhanced thermal stability. © 2019 Society of Chemical Industry