Integration of Functional Groups to Enhance the Solubility and Stability of Viologen in Aqueous Organic Redox Flow Batteries.

The chemical stability and energy density of redox couples are crucial factors in enhancing the durability and cost competitiveness of aqueous flow batteries. This study proposed integrating functional groups to viologen anolyte to increase its solubility and, consequently, energy density and stability for prolonged performance. Specifically, sulfonate and ester groups were selectively incorporated at the nitrogen sites of viologen to enhance solubility, leveraging their asymmetry and double hydrophilicity. Furthermore, an alpha-methyl group was introduced between the bipyridine and ester groups to enhance the chemical stability by preventing stacking and dimerization that can lead to irreversible degradation. The modified viologen demonstrated a remarkable solubility of 3.0 M in deionized water, corresponding to a volumetric capacity of 80.404 Ah L-1. Additionally, the designed viologen exhibits outstanding retention of 92.4% after 200 cycles with a minimal capacity fading rate of 0.055% per cycle in a 0.1 M flow cell test.

Beyond Slurry-Cast Supercapacitor Electrodes: PAN/MWNT Heteromat-Mediated Ultrahigh Capacitance Electrode Sheets.

Supercapacitors (SCs) have garnered considerable attention as an appealing power source for forthcoming smart energy era. An ultimate challenge facing the SCs is the acquisition of higher energy density without impairing their other electrochemical properties. Herein, we demonstrate a new class of polyacrylonitrile (PAN)/multi-walled carbon tube (MWNT) heteromat-mediated ultrahigh capacitance electrode sheets as an unusual electrode architecture strategy to address the aforementioned issue. Vanadium pentoxide (V2O5) is chosen as a model electrode material to explore the feasibility of the suggested concept. The heteromat V2O5 electrode sheets are produced through one-pot fabrication based on concurrent electrospraying (for V2O5 precursor/MWNT) and electrospinning (for PAN nanofiber) followed by calcination, leading to compact packing of V2O5 materials in intimate contact with MWNTs and PAN nanofibers. As a consequence, the heteromat V2O5 electrode sheets offer three-dimensionally bicontinuous electron (arising from MWNT networks)/ion (from spatially reticulated interstitial voids to be filled with liquid electrolytes) conduction pathways, thereby facilitating redox reaction kinetics of V2O5 materials. In addition, elimination of heavy metallic foil current collectors, in combination with the dense packing of V2O5 materials, significantly increases (electrode sheet-based) specific capacitances far beyond those accessible with conventional slurry-cast electrodes.

Preparation of a reduced graphene oxide wrapped lithium-rich cathode material by self-assembly.

A lithium-rich cathode material wrapped in sheets of reduced graphene oxide (RGO) and functionalized with polydiallyldimethylammonium chloride (PDDA) was prepared by self-assembly induced from the electrostatic interaction between PDDA-RGO and the Li-rich cathode material. At current densities of 1000 and 2000 mA g(-1), the PDDA-RGO sheet wrapped samples demonstrated increased discharge capacities, increasing from 125 to 155 mA h g(-1) and from 82 to 124 mA h g(-1), respectively. The decreased resistance implied by this result was confirmed from electrochemical impedance spectroscopy results, wherein the charge-transfer resistance of the pristine sample decreased after wrapping with the PDDA-RGO sheets. The PDDA-RGO sheets served as a protective layer sand as a conductive material, which resulted in an improvement in the retention capacity from 56 to 81% after 90 cycles.

Economic feasibility of ethanol production from biomass and waste resources via catalytic reaction.

An economic evaluation of ethanol (EtOH) production from a thermo-chemical process derived from biomass/waste feedstocks was conducted. The influence of feed amounts, catalytic conversions, and EtOH selling prices was examined as these are the major variables for the economic evaluation of biomass/wastes conversion to EtOH. Among the three feedstock systems of biomass, high-moisture municipal solid waste (MSW), and plastic waste, the plastic waste has far better economic feasibility, with a payback period of 2-5 years at maximum CO conversion (40%) from syngas to ethanol, due to its higher heating value in comparison with biomass and high-moisture MSW. The heating value of the feedstock is a key factor in determining the overall economic efficiency in a thermo-chemical EtOH production system. Furthermore, enhancement of the CO conversion (related to catalytic activity) from syngas to EtOH using a low cost catalyst is necessary to retain economic efficiency because the CO conversion and cost consideration of catalyst are crucial factors to reduce the payback period.

Mesoporous carbide-derived carbon for cytokine removal from blood plasma.

Porous carbons can be used for purification of bio-fluids due to their excellent biocompatibility with blood. Since the ability to adsorb a range of inflammatory cytokines within the shortest possible time is crucial to stop the progression of sepsis, the improvement of the adsorption rate is a key factor to achieving efficient removal of cytokines. Here, we demonstrate the effect of synthesis temperatures (from 600 degrees C to 1200 degrees C), carbon particle sizes (from below 35 microm to 300 microm), and annealing conditions (Ar, NH(3), H(2), Cl(2), and vacuum annealing) that determine the surface chemistry, on the ability of carbide-derived carbons (CDCs) to remove cytokines TNF-alpha, IL-6, and IL-1 beta from blood plasma. Optimization of CDC processing and structure leads to up to two orders of magnitude increase in the adsorption rate. Mesoporous CDCs that were produced at 800 degrees C from Ti(2)AlC with the precursor particle size of <35 microm and annealed in NH(3), displayed complete removal of large molecules of TNF-alpha in less than an hour, with >85% and >95% TNF-alpha removal in 5 and 30 min, respectively. This is a very significant improvement compared to the previously published results for CDC (90% TNF-alpha removal after 1h) and activated carbons. Smaller interleukin IL-6 and IL-1 beta molecules can be completely removed within 5 min. These differences in adsorption rates show that carbons with controlled porosity can also be used for separation of protein molecules.

Magnetic transition and long-time relaxation behavior induced by selective injection of guest molecules into clathrate hydrates.

Magnetic molecules physisorbed into low-dimensional nanostructures of microporous materials such as graphite and metal-organic frameworks have been verified to exhibit an unusual magnetic behavior. We demonstrate that the selective injection of both magnetic and nonmagnetic guest molecules into the water-ice cages of clathrate hydrates to form a 3D superstructure with tetrahedral and diamond-like sublattices can modify the inherent magnetism.

Effect of interlayer ions on methane hydrate formation in clay sediments.

Natural methane hydrates occurring in marine clay sediments exhibit heterogeneous phase behavior with high complexity, particularly in the negatively charged interlayer region. To date, the real clay interlayer effect on natural methane hydrate formation and stability remains still much unanswered, even though a few computer simulation and model studies are reported. We first examined the chemical shift difference of 27Al, 29Si, and 23Na between dry clay and clay containing intercalated methane hydrates (MH) in the interlayer. We also measured the solid-state 13C MAS NMR spectra of MH in Na-montmorillonite (MMT) and Ca-montmorillonite (MMT) to reveal abnormal methane popularity established in the course of intercalation and further performed cryo-TEM and XRD analyses to identify the morphology and layered structure of the intercalated methane hydrate. The present findings strongly suggest that the real methane amount contained in natural MH deposits should be reevaluated under consideration of the compositional, structural, and physical characteristics of clay-rich sediments. Furthermore, the intercalated methane hydrate structure should be seriously considered for developing the in situ production technologies of the deep-ocean methane hydrate.

Spectroscopic observation of atomic hydrogen radicals entrapped in icy hydrogen hydrate.

A hydrogen molecule entrapped in the cages of icy hydrogen hydrate is confined in host water framework and thus behaves unlike pure solid or liquid hydrogen. The gamma-irradiated hydrogen radicals are for the first time observed from ESR and solid-state MAS 1H NMR spectra to stably exist in the icy hydrate channels without any collapse of the host framework, confirming the chemical shift consistency of ionized hydrogen derivatives. We discuss the confined icy hydrate channels, which can act as potential storage sites for simultaneously imprisoning both molecular and ionized hydrogen and further as icy nanoreactors.

Thermal expansivity of tetrahydrofuran clathrate hydrate with diatomic guest molecules.

The guest dynamics and thermal behavior occurring in the cages of clathrate hydrates appear to be too complex to be clearly understood through various structural and spectroscopic approaches, even for the well-known structures of sI, sII, and sH. Neutron diffraction studies have recently been carried out to clarify the special role of guests in expanding the host water lattices and have contributed to revealing the influence factors on thermal expansivity. Through this letter we attempt to address three noteworthy features occurring in guest inclusion: (1) the effect of guest dimension on host water lattice expansion; (2) the effect of thermal history on host water lattice expansion; and (3) the effect of coherent/incoherent scattering cross sections on guest thermal patterns. The diatomic guests of H 2, D 2, N 2, and O 2 have been selected for study, and their size and mass dependence on the degree of lattice expansion have been examined, and four sII clathrate hydrates with tetrahydrofuran (THF) have been synthesized in order to determine their neutron powder diffraction patterns. After thermal cycling, the THF + H 2 clathrate hydrate is observed to exhibit an irreversible plastic deformation-like pattern, implying that the expanded lattices fail to recover the original state by contraction. The host-water cage dimension after degassing the guest molecules remains as it was expanded, and thus host-guest as well as guest-guest interactions will be altered if guest uptake reoccurs.

Structure transition and swapping pattern of clathrate hydrates driven by external guest molecules.

We first report here that under strong surrounding gas of external CH4 guest molecules the sII and sH methane hydrates are structurally transformed to the crystalline framework of sI, leading to a favorable change of the lattice dimension of the host-guest networks. The high power decoupling 13C NMR and Raman spectroscopies were used to identify structure transitions of the mixed CH4 + C2H6 hydrates (sII) and hydrocarbons (methylcyclohexane, isopentane) + CH4 hydrates (sH). The present findings might be expected to provide rational evidences regarding the preponderant occurrence of naturally occurring sI methane hydrates in marine sediments. More importantly, we note that the unique and cage-specific swapping pattern of multiguests is expected to provide a new insight for better understanding the inclusion phenomena of clathrate materials.

Characterization of PVdF(HFP) gel electrolytes based on 1-(2-Hydroxyethyl)-3-methyl imidazolium ionic liquids.

Poly(vinylidenefluoride)-hexafluoropropylene (PVdF(HFP))-ionic liquid gel electrolytes were prepared using ionic liquids based on 1-(2-hydroxyethyl)-3-methyl imidazolium tetrafluoroborate and 1-(2-hydroxyethyl)-3-methyl imidazolium hexafluorophosphate. A conventional metathesis reaction was used to prepare these ionic liquids, which have high purity and exhibit a liquid state at room temperature. The prepared polymer-ionic liquid gel proved to be a free-standing and rubbery film in which the degree of transparency differed according to the ratio and type of ionic liquid used. TGA and FTIR analyses confirmed that the solvent, N,N-Dimethylacetamide (DMAC), used for mixing PVdF(HFP) polymer with ionic liquid was almost totally removed during the gelling and drying processes. SEM photographs were taken of the surface structure of the PVdF(HFP)-ionic liquid gel in order to evaluate the morphology of the film's surface according to the mixing ratio and the nature of the ionic liquid. The thermal behaviors of PVdF(HFP)-ionic liquid gels were observed to be similar to those of neat ionic liquids through DSC analysis, and the compatibility between the polymer and ionic liquid was investigated by XRD analysis. The ionic conductivities of all the gels were 10(-3)-10(-5) S cm(-1) in a temperature range of 20-70 degrees C.