As a cleaner, cheaper, and more globally evenly distributed fuel, natural gas has considerable environmental, economic, and political advantages over petroleum as a source of energy for the transportation sector. Despite these benefits, its low volumetric energy density at ambient temperature and pressure presents substantial challenges, particularly for light-duty vehicles with little space available for on-board fuel storage. Adsorbed natural gas systems have the potential to store high densities of methane (CH4, the principal component of natural gas) within a porous material at ambient temperature and moderate pressures. Although activated carbons, zeolites, and metal-organic frameworks have been investigated extensively for CH4 storage, there are practical challenges involved in designing systems with high capacities and in managing the thermal fluctuations associated with adsorbing and desorbing gas from the adsorbent. Here, we use a reversible phase transition in a metal-organic framework to maximize the deliverable capacity of CH4 while also providing internal heat management during adsorption and desorption. In particular, the flexible compounds Fe(bdp) and Co(bdp) (bdp(2-) = 1,4-benzenedipyrazolate) are shown to undergo a structural phase transition in response to specific CH4 pressures, resulting in adsorption and desorption isotherms that feature a sharp 'step'. Such behaviour enables greater storage capacities than have been achieved for classical adsorbents, while also reducing the amount of heat released during adsorption and the impact of cooling during desorption. The pressure and energy associated with the phase transition can be tuned either chemically or by application of mechanical pressure.
Since 1987, high-luminance low-voltage driven devices based on tris(8-hydroxyquinoline)aluminum(III) (Alq 3 ) opened the route to design low-cost large area displays and illuminators. Despite the large number of studies devoted to this material, very little is known about its basic structural and optical properties in the solid state. Therefore, we have investigated the structure(s) and the correlation between intermolecular interactions and optical properties in various Alq 3 systems, including solution, amorphous thin films, and different crystalline forms. Two novel unsolvated polymorphs of Alq 3 , namely, R-Alq 3 and -Alq 3 , have been synthesized and their crystalline structures determined from X-ray diffraction data on powders (R) and single crystals ( ). Crystals of R-Alq 3 are triclinic, space group P-1, a ) 6.2586 (8) Å, b ) 12.914(2) Å; c ) 14.743(2) Å, R ) 109.66(1)°; ) 89.66(1)°, and γ ) 97.68(1)°; crystals of -Alq 3 are triclinic, space group P-1, a ) 8.4433(6) Å, b ) 10.2522(8) Å; c ) 13.1711(10) Å, R ) 108.578(1)°, ) 97.064(1)°, and γ ) 89.743 (1)°. Both these crystal structures consist of a racemic mixture of the mer isomer, but are characterized by different molecular packings involving well-defined short contacts between quinoxaline ligands belonging to symmetry-related Alq 3 molecules with interligand spacings in the 3.5-3.9 Å range. A third "high-temperature" phase, γ-Alq 3 , was found to contain orientationally disordered mer-Alq 3 molecules, lying about a 32 position of the trigonal P-31c space group, with a ) 14.41(1) Å and c ) 6.22(1) Å. In addition, a hemichlorobenzene adduct of Alq 3 was also prepared and structurally characterized (monoclinic, space group P2 1 /n, a ) 10.786(1) Å, b ) 13.808(2) Å, c ) 16.928(2) Å, ) 97.90(2)°). Investigations of the different crystal phases, as well as of amorphous thin films and solutions by absorption, fluorescence excitation, fluorescence, and Raman spectroscopy, allowed the effect of the molecular packing on the emission properties to be elucidated, the nature of the photoexcitations to be clarified, and the vibrational fingerprints of the R and crystalline forms to be highlighted. The spectral position of fluorescence is found to be correlated with both the molecular density of the packing and the length of interligand contacts between neigboring Alq 3 molecules as a consequence of different dispersive and dipolar interactions as well as different π-π orbital overlaps (the shorter the contacts, i.e., the denser the crystal, the more the fluorescence is red-shifted). The low-temperature (4.2 K) vibronic structure of the fluorescence spectrum of Alq 3 is resolved for the first time. It is assigned to the FranckCondon activity of an in-plane bending mode at ca. 525 cm -1 , and it is symptomatic of the ligand-centered nature of the optical transitions. From the analysis of the vibronic progression the existence of a strong electronphonon coupling involving the 525 cm -1 mode with a Huang-Rhys factor of ca. 2.6 ( 0.4 is inferred. The origin of the amorp...
Colloidal nanocrystals (NCs) of APbX3-type lead halide perovskites [A = Cs+, CH3NH3+ (methylammonium or MA+) or CH(NH2)2+ (formamidinium or FA+); X = Cl–, Br–, I–] have recently emerged as highly versatile photonic sources for applications ranging from simple photoluminescence down-conversion (e.g., for display backlighting) to light-emitting diodes. From the perspective of spectral coverage, a formidable challenge facing the use of these materials is how to obtain stable emissions in the red and infrared spectral regions covered by the iodide-based compositions. So far, red-emissive CsPbI3 NCs have been shown to suffer from a delayed phase transformation into a nonluminescent, wide-band-gap 1D polymorph, and MAPbI3 exhibits very limited chemical durability. In this work, we report a facile colloidal synthesis method for obtaining FAPbI3 and FA-doped CsPbI3 NCs that are uniform in size (10–15 nm) and nearly cubic in shape and exhibit drastically higher robustness than their MA- or Cs-only cousins with similar sizes and morphologies. Detailed structural analysis indicated that the FAPbI3 NCs had a cubic crystal structure, while the FA0.1Cs0.9PbI3 NCs had a 3D orthorhombic structure that was isostructural to the structure of CsPbBr3 NCs. Bright photoluminescence (PL) with high quantum yield (QY > 70%) spanning red (690 nm, FA0.1Cs0.9PbI3 NCs) and near-infrared (near-IR, ca. 780 nm, FAPbI3 NCs) regions was sustained for several months or more in both the colloidal state and in films. The peak PL wavelengths can be fine-tuned by using postsynthetic cation- and anion-exchange reactions. Amplified spontaneous emissions with low thresholds of 28 and 7.5 μJ cm–2 were obtained from the films deposited from FA0.1Cs0.9PbI3 and FAPbI3 NCs, respectively. Furthermore, light-emitting diodes with a high external quantum efficiency of 2.3% were obtained by using FAPbI3 NCs.
Metal-organic frameworks can offer pore geometries that are not available in zeolites or other porous media, facilitating distinct types of shape-based molecular separations. Here, we report Fe2(BDP)3 (BDP(2-) = 1,4-benzenedipyrazolate), a highly stable framework with triangular channels that effect the separation of hexane isomers according to the degree of branching. Consistent with the varying abilities of the isomers to wedge along the triangular corners of the structure, adsorption isotherms and calculated isosteric heats indicate an adsorption selectivity order of n-hexane > 2-methylpentane > 3-methylpentane > 2,3-dimethylbutane ≈ 2,2-dimethylbutane. A breakthrough experiment performed at 160°C with an equimolar mixture of all five molecules confirms that the dibranched isomers elute first from a bed packed with Fe2(BDP)3, followed by the monobranched isomers and finally linear n-hexane. Configurational-bias Monte Carlo simulations confirm the origins of the molecular separation.
Bright green emitters with adjustable photoluminescence (PL) maxima in the range of 530–535 nm and full-width at half-maxima (fwhm) of <25 nm are particularly desirable for applications in television displays and related technologies. Toward this goal, we have developed a facile synthesis of highly monodisperse, cubic-shaped formamidinium lead bromide nanocrystals (FAPbBr3 NCs) with perovskite crystal structure, tunable PL in the range of 470–540 nm by adjusting the nanocrystal size (5–12 nm), high quantum yield (QY) of up to 85% and PL fwhm of <22 nm. High QYs are also retained in films of FAPbBr3 NCs. In addition, these films exhibit low thresholds of 14 ± 2 μJ cm–2 for amplified spontaneous emission.
Crystal defects in highy luminescent colloidal nanocrystals (NCs) of CsPbX3 perovskites (X = Cl, Br, I) are investigated. Here, using X-ray total scattering techniques and the Debye scattering equation (DSE), we provide evidence that the local structure of these NCs always exhibits orthorhombic tilting of PbX6 octahedra within locally ordered subdomains. These subdomains are hinged through a two-/three-dimensional (2D/3D) network of twin boundaries through which the coherent arrangement of the Pb ions throughout the whole NC is preserved. The density of these twin boundaries determines the size of the subdomains and results in an apparent higher-symmetry structure on average in the high-temperature modification. Dynamic cooperative rotations of PbX6 octahedra are likely at work at the twin boundaries, causing the rearrangement of the 2D or 3D network, particularly effective in the pseudocubic phases. An orthorhombic, 3D γ-phase, isostructural to that of CsPbBr3 is found here in as-synthesized CsPbI3 NCs.
Reactions between the tritopic pyrazole-based ligand 1,3,5-tris(1H-pyrazol-4-yl)benzene (H3BTP) and transition metal acetate salts in DMF afford microporous pyrazolate-bridged metal–organic frameworks of the type M3(BTP)2*xsolvent (M = Ni (1), Cu, (2), Zn (3), Co (4)). Ab-initio X-ray powder diffraction methods were employed in determining the crystal structures of these compounds, revealing 1 and 2 to exhibit an expanded sodalite-like framework with accessible metal cation sites, while 3 and 4 possess tetragonal frameworks with hydrophobic surfaces and narrower channel diameters. Compounds 1–4 can be Desolvated without loss of crystallinity by heating under dynamic vacuum, giving rise to microporous solids with BET surface areas of 1650, 1860, 930 and 1027 m2/g, respectively. Thermogravimetric analyses and powder X-ray diffraction measurements demonstrate the exceptional thermal and chemical stability of these frameworks. In particular, 3 is stable to Heating in air up to at least 510 °C, while 1 is stable to heating in air to 430 °C, as well as to treatment with boiling aqueous solutions of pH 2 to 14 for two weeks. Unexpectedly, 2 and 3 are converted into new crystalline metal–organic frameworks upon heating in boiling water. With the combination of stability under extreme conditions, high surface area, and exposed metal sites, it is anticipated that 1 may open the way to testing metal–organic frameworks for catalytic processes that currently employ zeolites
In this communication, a series of observations and data analyses coherently confirms the suitability of the novel metal-organic framework (MOF) [Zn(4)(μ(4)-O)(μ(4)-4-carboxy-3,5-dimethyl-4-carboxy-pyrazolato)(3)] (1) in the capture of harmful volatile organic compounds (VOCs). It is worthy of attention that 1, whose crystal structure resembles that of MOF-5, exhibits remarkable thermal, mechanical, and chemical stability, as required if practical applications are sought. In addition, it selectively captures harmful VOCs (including models of Sarin and mustard gas, which are chemical warfare agents), even in competition with ambient moisture (i.e., under conditions mimicking operative ones). The results can be rationalized on the basis of Henry constant and adsorption heat values for the different essayed adsorbates as well as H(2)O/VOC partition coefficients as obtained from variable-temperature reverse gas chromatography experiments. To further strengthen the importance of 1, its performance in the capture of harmful VOCs has been compared with those of well-known materials, namely, a MOF with coordinatively unsaturated metal sites, [Cu(3)(btc)(2)] and the molecular sieve active carbon Carboxen. The results of this comparison show that coordinatively unsaturated metal sites (preferential guest-binding sites) are ineffective for the capture of VOCs in the presence of ambient moisture. Consequently, we propose that the driving force of the VOC-MOF recognition process is mainly dictated by pore size and surface hydrophobicity.
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