A new Li-Al-N-H system for reversible hydrogen storage

Complex metal hydrides are considered as a class of candidate materials for hydrogen storage. Lithium-based complex hydrides including lithium alanates (LiAlH(4) and Li(3)AlH(6)) are among the most promising materials owing to its high hydrogen content. In the present work, we investigated dehydrogenation/rehydrogenation reactions of a combined system of Li(3)AlH(6) and LiNH(2). Thermogravimetric analysis (TGA) of Li(3)AlH(6)/3LiNH(2)/4 wt % TiCl(3)-(1)/(3)AlCl(3) mixtures indicated that a large amount of hydrogen (approximately 7.1 wt %) can be released between 150 degrees C and 300 degrees C under a heating rate of 5 degrees C/min in two dehydrogenation reaction steps. The results also show that the dehydrogenation reaction of the new material system is nearly 100% reversible under 2000 psi pressure hydrogen at 300 degrees C. Further, a short-cycle experiment has demonstrated that the new combined material system of alanates and amides can maintain its hydrogen storage capacity upon cycling of the dehydrogenation/rehydrogenation reactions.     

A new donor-acceptor molecule with uniaxial anisotropy for efficient vacuum-deposited organic solar cells

A new D-π-A molecule (TPDCDTS) adopting coplanar diphenyl-substituted dithienosilole as a central π-bridge of triphenylamine (donor) and dicyanovinylene (acceptor) has been synthesized as donor material for small molecule organic solar cells (SMOSC) incorporating C(70) as an acceptor showed an appreciable power conversion efficiency of 3.82%.     

Modified lithium borohydrides for reversible hydrogen storage

In an attempt to develop lithium borohydrides as reversible hydrogen storage materials with high hydrogen storage capacities, the feasibility of reducing the dehydrogenation temperature of the lithium borohydride and moderating rehydrogenation conditions was explored. The lithium borohydride was modified by ball milling with metal oxides and metal chlorides as additives. The modified lithium borohydrides released 9 wt % hydrogen starting from 473 K. The dehydrided modified lithium borohydrides absorbed 7-9 wt % hydrogen at 873 K and 7 MPa. The modification with additives reduced the dehydriding starting temperature from 673 to 473 K and moderated the rehydrogenation conditions from 923 K/15 MPa to 873 K/7 MPa. XRD and SEM analysis revealed the formation of an intermediate compound that might play a key role in changing the reaction path, resulting in the lower dehydriding temperature and reversibility. The reversible hydrogen storage capacity of the oxide-modified lithium borohydrides decreased gradually during hydriding/dehydriding cycling. One of the possible reasons for this effect might be the loss of boron during dehydrogenation, but this can be prevented by changing the dehydriding path using appropriate additives. The additives reduced the dehydriding temperature and improved the reversibility, but they also reduced the hydrogen storage capacity. The best compromise can be reached by selecting appropriate additives, optimizing the additive loading, and using new synthesis processes other than ball milling.     

Phototriggered color modulation of perovskite nanoparticles for high density optical data storage

Photoresponsive luminescent materials (PLMs) have attracted much attention in various optoelectronic fields, especially in optical data storage. Multi-wavelength (N-wavelength) based optical storage is a promising approach to increase the data storage density, but its current application is limited by the fact that most PLMs have only two-wavelength emissive states after certain light excitation, which requires simultaneous use of several PLMs and different irradiation light sources. In this study, we discovered that the wavelength of perovskite nanocrystals (PNCs) in the presence of dichloromethane (DCM) could be continuously and precisely tuned over a very wide color range (from red to violet) with the help of a single UV light source. The changes in crystal structures and optical properties of PNCs during UV irradiation were investigated in detail; the effects of capping ligand, solvent, UV irradiation power and time were evaluated, and the mechanism of UV triggered PNC fluorescence change was studied and is discussed. Finally, the applicability of PNCs/DCM film in N-wavelength-based high-density optical data storage was verified.

The perovskite nanocrystals-dichloromethane (PNCs-DCM) with tunable fluorescent color under UV light are a new kind of photoresponsive luminescent materials (PLMs), which are qualified to apply in optical data storage.     

Synthesis, cyclic voltammetric studies, and electrogenerated chemiluminescence of a new phenylquinoline-biphenothiazine donor-acceptor molecule

We report the synthesis, electrochemistry, and luminescence of a novel ECL emitting compound containing two electron-accepting hexyl-phenylquinoline groups covalently attached to the 3,3'-positions of the electron-donating 10,10'-dimethylbiphenothiazine group. The optimized geometry as determined from semiempirical MNDO calculations shows that the two quinoline groups are twisted 82.5 degrees from the two phenothiazine rings, indicating a lack of electron delocalization among these groups. This unique geometry allows generation of localized radical cations and radical anions capable of generating ECL upon annihilation. However, the phenothiazine rings are twisted 46.5 degrees relative to each other, suggesting possible interactions between the two moieties. This is evident in the electrochemical behavior in which two closely spaced one-electron oxidations, rather than a single two-electron oxidation wave, were observed. The photophysical properties of BHQ-BPZ show strong resemblances to the parent compound, BPQ-PTZ, which contains a single phenothiazine moiety. In addition, the ECL spectrum produced via radical ion annihilation shows good agreement with the fluorescence emission of the compound.     

Intramolecular electron transfer within a covalent, fixed-distance donor-acceptor molecule in an ionic liquid

Intramolecular photoinduced charge separation and recombination within the donor-acceptor molecule 4-(N-pyrrolidino)naphthalene-1,8-imide-pyromellitimide, 5ANI-PI, are studied using ultrafast transient absorption spectroscopy in the room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [EMIM][Tf2N]. The rate constants of both photoinduced charge separation and charge recombination for 5ANI-PI in [EMIM][Tf2N] are comparable to those observed in pyridine, which has a static dielectric constant similar to that of [EMIM][Tf2N] but a viscosity that is nearly 2 orders of magnitude lower than that of [EMIM][Tf2N]. The electron-transfer dynamics of 5ANI-PI in [EMIM][Tf2N] are compared to those in pyridine as a function of temperature and are discussed in the context of recently reported ionic liquid solvation studies.     

A permanent optical storage medium exhibiting ultrahigh contrast, superior stability, and a broad working wavelength regime

In this paper we demonstrate an optical storage medium having advantages of ultrahigh contrast, superior stability, and broadband working wavelengths. Combining a single shot of deep-ultraviolet (UV) laser illumination with a Au particle-assisted etching process, we formed broadband antireflective, one-dimensional silicon nanowire arrays (SiNWs) with selectively at specific positions. Optical measurements and three-dimensional finite-difference time domain (3D-FDTD) simulations revealed ultrahigh reflection contrast between the Au and the SiNWs for both far- and near-field regimes. Relative to typical organic-based storage media, Au films and SiNWs are more stable, both chemically and thermally; therefore, we suspect that this new storage medium would exhibit high stability toward moisture, sunshine, and elevated temperatures.     

A gas- and condensed-phase density functional study of donor-acceptor complexes of sulfur trioxide

A series of donor-acceptor complexes containing sulfur trioxide have been studied in the gas and condensed phases using density functional theory. The condensed phase is represented using the polarizable continuum model. The systems investigated include complexes of nitrogen-containing donor molecules, (CH(3))(n)H(3-n)N (n = 0-3), with SO(3) and complexes of oxygen-containing donor molecules, (CH(3))(m)H(2-m)O (m = 0-2), with SO(3). Significant differences are observed between the gas- and condensed-phase properties of the complexes as a result of the ability of the condensed-phase medium to support higher charge separation between the donor and acceptor. The gas/condensed-phase behavior of two nitrogen-containing complexes, (CH(3))H(2)N-SO(3) and (CH(3))(2)HN-SO(3), has been investigated for the first time. These complexes exhibit properties intermediate to the previously observed H(3)N-SO(3) and (CH(3))(3)N-SO(3) complexes. Systematic trends in the gas- and condensed-phase structure and properties have been observed as methyl groups are added to the donor molecule. In addition, two oxygen-containing complexes, CH(3)OH-SO(3) and (CH(3))(2)O-SO(3), have been characterized for the first time. The differences between the gas- and condensed-phase properties of the oxygen-containing complexes are, in many cases, larger than those of the nitrogen-containing complexes, and therefore they represent an intriguing new class of complexes for potential experimental observation. Finally, a strong correlation between the charge transfer and binding energy has been obtained for both the nitrogen- and oxygen-containing complexes of sulfur trioxide.     

UV‐photodimerization in uracil‐substituted dendrimers for high density data storage

Two series of uracil‐functionalized dendritic macromolecules based on poly (amidoamine) PAMAM and 2,2‐bis(hydroxymethylpropionic acid) bis‐MPA backbones were prepared and their photoinduced (2π+2π) cycloaddition reactions upon exposure to UV light at 257 nm examined. Dendrimers up to 4th generation were synthesized and investigated as potential materials for high capacity optical data storage with their dimerization efficiency compared to uracil as a reference compound. This allows the impact of increasing the generation number of the dendrimers, both the number of chromophores, as well as the different steric environments, on the performance of each series of dendrimers to be investigated. The (uracil)₁₂‐[G‐2]‐bis‐MPA and (uracil)₈‐[G‐1]‐PAMAM were observed to have high dimerization efficiency in solution with different behavior being observed for the PAMAM and bis‐MPA dendrimers. The dendrimers with the best dimerization efficiency in solution were then examined in the solid state as thin films cast on quartz plates, and their film qualities along with their photodimerization performance studied. High quality films with a transmission response of up to 70% in 55 s. when irradiated at 257 nm with an intensity of 70 mW/cm² could be obtained suggesting future use as recording media for optical data storage. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4401–4412, 2007     

A quest for stable 2,2,9,9-tetrahaloplumbacyclonona-3,5,7-trienylidenes at density functional theory

In contrast to cyclonona-3,5,7-trienylidene (1_H) which turns out as a boat-shaped transition state for having a negative force constant, its heavier plumbylenic analogous (2_X) where X = H, F, Cl, Br, and I emerge as boat-shaped minima. This unsubstituted carbene has a triplet ground state while exclusive of 2_I which initially takes on a triplet multiplicity and eventually transforms to a less stable intramolecular ring opening product; all of the plumbylenes (2_H, 2_F, 2_Cl, and 2_Br) have a singlet ground state. Hence, stability anticipated by the singlet (S)–triplet (T) splitting (ΔE_S-T) decreases by going down in the group 17 column: 2_Br > 2_Cl > 2_F > 2_H > 1_H > 2_I. Also, the HOMO-LUMO gap (ΔE_HOMO-LUMO) increases as a result of substituting. From a thermodynamic perspective, our scrutinized 2_Br, 2_Cl, and 2_F are found 1.5–2 times more stable than that of the reported cyclopenta-2,4-dienplumbylene and 2,5-bis(halobora)-cyclopentenplumbylenes analogues, respectively. From a kinetic perspective, these nine-membered plumbylenes are found 20–26 kcal/mol more stable than that of their corresponding five-membered congeners. The NBO analysis on stable singlet 2_Br shows that there is a mesomeric interaction between bromine lone-pair electron and the Pb divalent atom of 2_Br with bonding (σ) and anti-bonding (σ^*) orbitals of carbon–bromine and carbon–lead. The main stabilizing effect appears to be π- and σ-bond hyperconjugation among the iodine heteroatom and divalent center of triplet 2_I. This research signifies the thermodynamic and kinetic stabilities of the biggest unsaturated cyclic plumbylenes hoping to prompt the experimental attention toward them.

     

Modified lithium borohydrides for reversible hydrogen storage (2)

This paper reports the results of the effort to destabilize lithium borohydride for reversible hydrogen storage. Various metals, metal hydrides, and metal chlorides were selected and evaluated as destabilization agents for reducing dehydriding temperatures and improving dehydriding/rehydriding reversibility. The most effective material was LiBH4 + 0.2MgCl2 + 0.1TiCl3 which starts desorbing 5 wt % of hydrogen at 60 degrees C and can be rehydrogenated to 4.5 wt % at 600 degrees C and 70 bar. X-ray diffraction and Raman spectroscopic analysis show the interaction of LiBH4 with additives and the unusual change of B-H stretching.     

Indirect, reversible high-density hydrogen storage in compact metal ammine salts

The indirect hydrogen storage capabilities of Mg(NH 3) 6Cl 2, Ca(NH 3) 8Cl 2, Mn(NH 3) 6Cl 2, and Ni(NH 3) 6Cl 2 are investigated. All four metal ammine chlorides can be compacted to solid tablets with densities of at least 95% of the crystal density. This gives very high indirect hydrogen densities both gravimetrically and volumetrically. Upon heating, NH 3 is released from the salts, and by employing an appropriate catalyst, H 2 can be released corresponding to up to 9.78 wt % H and 0.116 kg H/L for the Ca(NH 3) 8Cl 2 salt. The NH 3 release from all four salts is investigated using temperature-programmed desorption employing different heating rates. The desorption is found mainly to be limited by heat transfer, indicating that the desorption kinetics are extremely fast for all steps. During desorption from solid tablets of Mg(NH 3) 6Cl 2, Mn(NH 3) 6Cl 2, and Ni(NH 3) 6Cl 2, nanoporous structures develop, which facilitates desorption from the interior of large, compact tablets. Density functional theory calculations reproduce trends in desorption enthalpies for the systems studied, and a mechanism in which individual chains of the ammines are released from the surface of the crystal is proposed to explain the fast absorption/desorption processes.     

Polyol-mediated synthesis of ultrafine tin oxide nanoparticles for reversible Li-ion storage

A simple, cheap and versatile, polyol-mediated fabrication method has been extended to the synthesis of tin oxide nanoparticles on a large scale. Ultrafine SnO₂ nanoparticles with crystallite sizes of less than 5 nm were realized by refluxing SnCl₂ · 2H₂O in ethylene glycol at 195 °C for 4 h under vigorous stirring in air. The as-prepared SnO₂ nanoparticles exhibited enhanced Li-ion storage capability and cyclability, demonstrating a specific capacity of 400 mAh g⁻¹ beyond 100 cycles.     

Incorporation of MWCNTs into leaf-like CuO nanoplates for superior reversible Li-ion storage

CuO/MWCNT nanocomposite is prepared by a simple precipitation method. The MWCNTs are incorporated into the leaf-like CuO nanoplates and build up a network to connect the CuO nanoleaves. The as-prepared CuO/MWCNT exhibits superior reversible Li-ion storage, the capacity maintains 627 mAh g^? 1 at 60 mA g^? 1 even after 50 cycles. The improved capability is ascribed to the MWCNT network in the composite, which improves the electrical contact of CuO/CuO and CuO/current collector, facilitates the charge transfer on CuO/electrolyte interfaces, and compensates the volume change of CuO during cycling.     

Liquid crystals for holographic optical data storage

A tutorial review is presented to inform and inspire the reader to develop and integrate strong scientific links between liquid crystals and holographic data storage, from a materials scientist's viewpoint. The principle of holographic data storage as a means of providing a solution to the information storage demands of the 21st century is detailed. Holography is a small subset of the much larger field of optical data storage and similarly, the diversity of materials used for optical data storage is enormous. The theory of polarisation holography which produces holograms of constant intensity, is discussed. Polymeric liquid crystals play an important role in the development of materials for holographic storage and photoresponsive materials based on azobenzene are targeted for discussion due to their ease of photo-reversion between trans- and cis-states. Although the final polymer may not be liquid crystalline, irradiation can induce ordered domains. The mesogens act in a co-operative manner, enhancing refractive indices and birefringences. Surface relief gratings are discussed as a consequence of holographic storage. Cholesteric polymers comprising azobenzene are briefly highlighted. Irradiation causing cis-trans-isomerisation can be used to control helix pitch. A brief mention of liquid crystals is also made since these materials may be of future interest since they are optically transparent and amenable to photo-induced anisotropy.     

Polymers for electrical and optical data storage

Polymers possess great significance in data storage technology. Taking as an example electrical and optical data storage, the state of development, properties required and opportunities for application of selected polymers are discussed, namely: (i) ferroelectric polymers with low switching voltages and extremely short switching times for electric data storage; and (ii) transparent polymers with low birefringence and high thermal stability for optical data storage. In the area of electrical data storage devices/memories, ferroelectric polymers have not been able to establish themselves up to now due to their long switching time and limited thermal stability. However, recent investigations show that suitable copolymers based on PVDF/TrFE copolymers in ultra-thin layers can achieve switching times of ≤100 ns. Nevertheless, the limited thermal stability of PVDF/TrFE copolymers prevent them from being integrated into the usual manufacturing process for Si-based data storage devices (D-RAM resp. S-RAM) and thereby frustrates the desired objective of producing nonvolatile random access memories (NV-RAMs). In the area of optical data storage technology, polycarbonate (PC) has established itself due to its favorable combination of properties. Thus, audio compact disks (CDs) are manufactured exclusively of PC, while high-flow PC types of high optical purity are clearly the preferred substrate material for optical data storage disks. The increasingly stringent requirements to be met in terms of lower birefringence and better thermal stability mean that the development of suitable modified or substituted polycarbonates is required. The development work being carried out worldwide in this area is reviewed here, and new suitable substituted polycarbonates with lower birefringence and significantly increased thermal stability up to glass temperatures of 238°C are presented. In addition, we deduce structure—property relationships for the above-mentioned structurally modified polycarbonates, specifically considering rotation potentials along the polymer backbone.     

Biological nano-ceramic materials for holographic data storage

Here we present, a two-photon absorption (2PA) study in Fe²⁺ and Fe³⁺ oxidation states of cytochrome c molecule in water solution, using the femtosecond Z-scan technique with pulses from 560 to 850 nm. No qualitative difference was observed in the 2PA process for the two Fe oxidation states. The 2PA cross-sections, for both samples, increase as the wavelength approaches the absorption band, in agreement with the resonant denominator in the sum-over states model, presenting a maximum value of approximately 1000 GM at about 600 nm.     

A biporous coordination framework with high H2 storage density

A biporous three dimensional (3,6)-connected coordination framework is reported which exhibits excellent H2 adsorption at low pressures (< or = 1 bar) with high H2 adsorption density.