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We are currently witnessing the dawn of hydrogen (H2) economy, where H2 will soon become a primary fuel for heating, transportation, and long-distance and long-term energy storage. Among diverse possibilities, H2 can be stored as a pressurized gas, a cryogenic liquid, or a solid fuel via adsorption onto porous materials. Metal-organic frameworks (MOFs) have emerged as adsorbent materials with the highest theoretical H2 storage densities on both a volumetric and gravimetric basis. However, a critical bottleneck for the use of H2 as a transportation fuel has been the lack of densification methods capable of shaping MOFs into practical formulations while maintaining their adsorptive performance. Here, we report a high-throughput screening and deep analysis of a database of MOFs to find optimal materials, followed by the synthesis, characterization, and performance evaluation of an optimal monolithic MOF (monoMOF) for H2 storage. After densification, this monoMOF stores 46 g L-1 H2 at 50 bar and 77 K and delivers 41 and 42 g L-1 H2 at operating pressures of 25 and 50 bar, respectively, when deployed in a combined temperature-pressure (25-50 bar/77 K ? 5 bar/160 K) swing gas delivery system. This performance represents up to an 80% reduction in the operating pressure requirements for delivering H2 gas when compared with benchmark materials and an 83% reduction compared to compressed H2 gas. Our findings represent a substantial step forward in the application of high-density materials for volumetric H2 storage applications.

peer-reviewed Hydrolytically stable adsorbents are needed for water vapor sorption related applications; however, design principles for porous materials with tunable water sorption behavior are not yet established. Here, we report that a platform of fourth-generation metal–organic materials (MOMs) with rigid frameworks and self-switching pores can adapt their pores to modulate water sorption. This platform is based upon the hydrolytically stable material CMOM-3S, which exhibits bnn topology and is composed of rod building blocks based upon S-mandelate ligands, 4,4-bipyridine ligands, and extraframework triflate anions. Isostructural variants of CMOM-3S were prepared using substituted R-mandelate ligands and exhibit diverse water vapor uptakes (20–67 cm3/g) and pore filling pressures (P/P0, 0.55–0.75). [Co2(R-4-Cl-man)2(bpy)3](OTf) (33R) is of particular interest because of its unusual isotherm. Insight into the different water sorption properties of the materials studied was gained from analysis of in situ vibrational spectra, which indicate self-switching pores via perturbation of extraframework triflate anions and mandelate linker ligands to generate distinctive water binding sites. Water vapor adsorption was studied using in situ differential spectra that reveal gradual singlet water occupancy followed by aggregation of water clusters in the channels upon increasing pressure. First-principles calculations identified the water binding sites and provide structural insight on how adsorbed water molecules affect the structures and the binding sites. Stronger triflate hydrogen bonding to the framework along with significant charge redistribution were determined for water binding in 33R. This study provides insight into a new class of fourth-generation (self-switching pores) MOM and the resulting effect upon water vapor sorption properties

We report the extraordinarily large positive magnetoresistances (MR, 69400% at 4.5 K under a magnetic field of 8.15 T), de Hass–van Alphen oscillations effect at 10 K and the semimetal-insulator-like transition in a wide range of temperature in highly oriented pyrolitic graphite (HOPG). Besides a dominating ordinary MR (OMR) mechanism in the free-electron mode, it is realized from qualitative analysis that the Coulomb interacting quasiparticles within graphite layers play some roles. However it is difficult to associate the transition with the simple OMR theory. In order to investigate the possible origins of the transition, further analysis is carried out. It is revealed that the magnetic-field-induced behaviour is responsible for the semimetal-insulator-like transitions in HOPG.

A sample of La0.833K0.167MnO3–SrTiO3 (LKMO/STO) is fabricated by the sol-gel method. The microstructure, magnetic and transportation properties have been studied. X-ray diffraction patterns indicate that the structure of LKMO/STO is a homogeneous solid solution phase. The resistivity of LKMO/STO shows the insulator behaviour, which is different from La0.833K0.167MnO3 (LKMO) whose resistivity shows metal–insulator transition with decreasing temperature. The low-field (m0H = 0.02 T) magnetoresistance decreases from 11% to 0.2% with the increasing temperature from 4 K to 220 K for the LKMO/STO sample. The magnitude of magnetoresistance in a strong field (μ0H = 5.5 T) almost increases linearly with decreasing temperature and reaches the maximum of 65% at the low temperature of 4.2 K, which is much higher than that of LKMO (40%). The enhanced low-field magnetoresistance effects are quantitatively explained by the spin-polarized tunnelling at grain boundaries.

The microstructure, magnetic and transport properties of the heterogeneous system with a nominal composition (1/m)Ag2O-La0.833K0.167MnO3 (1/m is molar ratio with m = 32, 16, 8, 4, and 2) have been studied. The x-ray diffraction patterns show that all the samples are two-phase composite and consist of a magnetic La0.833K0.167MnO3 (LKMO) perovskite phase and a nonmagnetic metal Ag phase. The room-temperature magnetoresistance (MR) effect is enhanced significantly due to the addition of Ag. For the m = 4 sample, we obtain MR values up to 32% under a lower field of 0.5 T and 67 % under a higher field of 5.5 T at the temperature of 300 K, which are much larger than the corresponding MR values (10% and 35%) of the LKMO sample without Ag. In the low-temperature range from 4.2 K to 250 K, the MR values of the Ag-added samples however decrease with the increasing Ag content in the samples. This effect is discussed qualitatively by using the relative contribution from the intrinsic MR effect and the extrinsic MR effect including the spin-polarized-tunnelling and spin-dependent scattering effects in different temperature regions.

The injection efficiency of spin-polarized quasi-particles in a superconducting Y-Ba-Cu-O (YBCO) film is investigated by means of current injection into the Nd0.7Sr0.3MnO3/SrTiO3/YBa2Cu3O7-δ heterostructures. We have successfully prepared six injection junction windows in the YBCO thin film strip, which are all 56 µm wide, but 80 µm, 40 µm, 20 µm, 10 µm, 5 µm, and 2 µm long, respectively. At 16 K, our YBCO thin film strip (80 nm thick) has Jc = 2×105A/cm2. Under the spin-polarized injection current of Iinj = 0.5 mA, with decreasing injection junction length L, injection efficiency η (η≡ΔJc/ΔJinj; ΔJc: the suppression of critical current density due to finite ΔJinj) increases gradually, until L is not more than 20 µm. In that case, η hardly varies with the change of L, reaching up to about 6. We think that these results are related to the spin diffusion length of spin-polarized quasi-particles in the superconducting thin film. In our heterostructures, the YBCO thin film keeps good superconductivity and the injection junction windows are of proper size, therefore, we have obtained relatively high injection efficiency of spin-polarized quasi-particles.

A series of (La1-xTbx)2/3Sr1/3MnO3 polycrystalline samples has been studied by means of x-ray diffraction, magnetostriction and thermal expansion measurements. It has been found that this series undergoes a phase transition from a rhombohedral to an orthorhombic form at the doping level x≈0.20 at room temperature accompanied by an anisotropic magnetostriction up to -50×10-6 under a magnetic field of 1T. The linear and volume magnetostrictions vary with chemical composition, even change sign. At T=80K, the magnetostrictions for the samples of x=0.20 and 0.40 exhibit different behaviours. The sample of x=0.20 has positive volume and linear magnetostrictions and a negative anisotropic magnetostriction, while the sample of x=0.40 has an opposite behaviour. The magnitude of volume magnetostriction for both the samples is essential (~10-4) at T=80K under a magnetic field of 4T. We conclude that these anomalous effects are due to the charge delocalization and the structural phase transition between orthorhombic and rhombohedral forms induced by the applied magnetic field.