New isoreticular metal-organic framework materials for high hydrogen storage capacity

We propose new isoreticular metal-organic framework (IRMOF) materials to increase the hydrogen storage capacity at room temperature. Based on the potential-energy surface of hydrogen molecules on IRMOF linkers and the interaction energy between hydrogen molecules, we estimate the saturation value of hydrogen sorption capacity at room temperature. We discuss design criteria and propose new IRMOF materials that have high gravimetric and volumetric hydrogen storage densities. These new IRMOF materials may have gravimetric storage density up to 6.5 wt % and volumetric storage density up to 40 kg H2/m3 at room temperature.     

Enhanced hydrogen storage capacity of high surface area zeolite-like carbon materials

We report the synthesis of zeolite-like carbon materials that exhibit well-resolved powder XRD patterns and very high surface area. The zeolite-like carbons are prepared via chemical vapor deposition (CVD) at 800 or 850 degrees C using zeolite beta as solid template and acetonitrile as carbon precursor. The zeolite-like structural ordering of the carbon materials is indicated by powder XRD patterns with at least two well-resolved diffraction peaks and TEM images that reveal well-ordered micropore channels. The carbons possess surface area of up to 3200 m2/g and pore volume of up to 2.41 cm3/g. A significant proportion of the porosity in the carbons (up to 76% and 56% for surface area and pore volume, respectively) is from micropores. Both TEM and nitrogen sorption data indicate that porosity is dominated by pores of size 0.6-0.8 nm. The carbon materials exhibit enhanced (and reversible) hydrogen storage capacity, with measured uptake of up to 6.9 wt % and estimated maximum of 8.33 wt % at -196 degrees C and 20 bar. At 1 bar, hydrogen uptake capacity as high as 2.6 wt % is achieved. Isosteric heat of adsorption of 8.2 kJ/mol indicates a favorable interaction between hydrogen and the surface of the carbons. The hydrogen uptake capacity observed for the zeolite-like carbon materials is among the highest ever reported for carbon (activated carbon, mesoporous carbon, CNTs) or any other (MOFs, zeolites) porous material.     

Mg1.8La0.2Ni-xNi nanocomposites for electrochemical hydrogen storage

Mg1.8La0.2Ni hydrogen storage alloy was ball-milled with Ni powder, leading to the formation of a nanocrystalline and amorphous microstructure with particle sizes less than 50 nm in diameter. Each sample was examined by transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). This structure was beneficial for the reduction of electrochemical impedance, as well as significant improvement of its discharge capacity, cycle life, and rate capability for electrochemical hydrogen storage in an alkaline solution. When the molar ratio (x) of Ni over Mg1.8La0.2Ni was equal to 2, the dehydriding capacity reached 2.55 wt % from electrochemical pressure-temperature isotherms (P-C-T). It was in good agreement with its initial discharge capacity, 716 mA*h/[g of (Mg1.8La0.2Ni)], observed from the electrochemical charge and discharge process. After 50 cycles, its discharge capacity still reached 381 mA*h/[g of (Mg1.8La0.2Ni)]. Further results showed that this composite had a promising high rate capability. At the current density of 1200 mA/g its discharge capacity reached 48% of its initial capacity.     

新型储氢材料及其热力学与动力学问题

氢能作为一种理想的二次能源受到了国内外科研工作者的广泛关注,研制可以在室温和较低压力下方便、安全、高效地储存氢能的材料是氢能发展的瓶颈.到目前为止,固态储氢材料以能量密度高及安全性好等优势被认为极具应用前景,其中以轻质元素构成的氢化物(包括硼氢化物/铝氢化物(可用通式A(MH4)n表示,其中A是碱金属(Li,Na,K)或碱土金属(Be,Mg,Ca);M是硼或铝;n=1～4)、氨基氢化物(如LiNH2等))、氨硼烷(NH3BH3)、金属有机骨架材料(MOFs)是新型储氢材料研究领域的热点,本文将着重就目前这几类储氢材料的研究当中所涉及到的一些热力学及动力学问题进行总结探讨.     

Fast hydrogenation kinetics of acridine as a candidate of liquid organic hydrogen carrier family with high capacity

正Hydrogen has been deemed as one of the most efficient energy carriers for a broad variety of industrial applications [1,2].Large-scale, low-cost hydrogen production, safe storage and delivery represent a tremendous technological challenge and have become a subject of intense research and development activities in the past few decades [3–5]. Today, in many parts of the world,     

Synthesis of zeolite-casted microporous carbons and their hydrogen storage capacity

Zeolite-casted microporous carbons (ZMiPCs) were synthesized using the replica casting method. The ZMiPC were also treated chemically by H(3)PO(4) (A-ZMiPC) or KOH (B-ZMiPC) impregnation, to investigate the effect of the acceptor-donor interaction on the hydrogen storage behaviors. The presence of functional groups of the modified ZMiPC surfaces was confirmed by X-ray photoelectron spectroscopy. The total acidity of the carbon surfaces was determined using the Boehm titration method. The microstructure was characterized by X-ray diffraction. The N(2)/77K adsorption/desorption isotherms were analyzed to characterize specific surface area, pore volume, and pore size distribution of the samples. The capacity of hydrogen adsorption was evaluated using a pressure-composition-temperature apparatus at 298K/100bar. From these results, the specific surface areas and micropore volume of ZMiPC increased more than two fold compared to the zeolite template. Meanwhile, the textural properties of A-ZMiPC and B-ZMiPC were decreased by the chemical treatments. Consequently, the largest hydrogen storage was obtained on A-ZMiPC, even though their textural properties had decreased, due to a charge induced dipole interaction between the modified carbon surface and hydrogen molecules.     

Rewritable multicolor fluorescent patterns for multistate memory devices with high data storage capacity

We report a branched polyethyleneimine (BPEI)-quantum dot (QD) based rewritable fluorescent system with a multicolor recording mode, in which BPEI is both QD-multicolor patterning "writer" and data erasing "remover". This method could write distinct colors from size-tailored QDs to represent large numbers of logic states for high data storage capacity.     

Silicon core-hollow carbon shell nanocomposites with tunable buffer voids for high capacity anodes of lithium-ion batteries

Silicon core-hollow carbon shell nanocomposites with controllable voids between silicon nanoparticles and hollow carbon shell were easily synthesized by a two-step coating method and exhibited different charge-discharge cyclability as anodes for lithium-ion batteries. The best capacity retention can be achieved with a void/Si volume ratio of approx. 3 due to its appropriate volume change tolerance and maintenance of good electrical contacts.     

Body temperature triggered shape-memory polymers with high elastic energy storage capacity

Shape-memory polymers (SMPs) that respond near body temperature are attracting broad interest, especially in the biomedical fields. In this study, the triggering temperature of poly(caprolactone) SMP networks is precisely adjusted by inclusion of non-crystallizable molecular linkers and by variation of prepolymer molecular weight. Longer, non-crystalline linkers and lower molecular weight prepolymers interfere with crystallization, lowering the transition temperature. Networks are prepared with crystallization temperatures that are beneath the human body temperature and yet are above room temperature. Upon cooling such amorphous networks to room temperature, crystallization is sluggish. There, elastomers can be easily strained by several hundred-percent to induce crystallization, thereby fixing strained states. If subsequently heated, programmed SMPs can release significant amounts of stored strain energy (∼3 MJ/m³). SMPs that combine elastic energy storage and exhibit triggering temperatures near the human body temperature could benefit emerging applications in the biomedical space. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1397–1404     

Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature

Metal-organic frameworks (MOFs) show high CO2 storage capacity at room temperature. Gravimetric CO2 isotherms for MOF-2, MOF-505, Cu3(BTC)2, MOF-74, IRMOFs-11, -3, -6, and -1, and MOF-177 are reported up to 42 bar. Type I isotherms are found in all cases except for MOFs based on Zn4O(O2C)6 clusters, which reveal a sigmoidal isotherm (having a step). The various pressures of the isotherm steps correlate with increasing pore size, which indicates potential for gas separations. The amine functionality of the IRMOF-3 pore shows evidence of relatively increased affinity for CO2. Capacities qualitatively scale with surface area and range from 3.2 mmol/g for MOF-2 to 33.5 mmol/g (320 cm3(STP)/cm3, 147 wt %) for MOF-177, the highest CO2 capacity of any porous material reported.     

Intensified electrochemical hydrogen storage capacity of multi-walled carbon nanotubes supported with Ni nanoparticles

The electrochemical hydrogen storage properties of Ni-supported multi-walled carbon nanotube (Ni/MWCNT) electrodes were investigated using charge/discharge (C&D) and cyclic voltammetry (CV) techniques. Nickel NPs were deposited on the MWCNT surface, which was first chemically oxidized by H₂SO₄ and HNO₃ (3:1, v/v). Hydrogen storage was carried out by using the Ni/MWCNT electrode as the working electrode in the electrochemical cell. A set of various current densities were applied to the cell to produce (C&D) cycles, and it became optimum corresponding to 1.5 mA current. According to the electrochemical test results, the highest electrochemical discharge capacity of 1625 mAh g^?1 was obtained for the electrode with ratio of 4:1 (MWCNTs to Ni) in the initial cycle, which corresponded to 6.07 wt% H₂. The storage capacity was increased and reached to 4909 mAh g^?1 (18.34 wt% H₂) after 20 cycles, and the electrode maintained the specific capacity as cycling continued. Thus, the Ni/MWCNT electrode displays an excellent cycle stability and a high capacity reversibility. CV measurements also showed that the electrochemical adsorption and desorption amount of hydrogen was increased by Ni loading onto the CNTs and indicated that the electrochemical hydrogen adsorption of the electrode has an activated period.     

Novel polymeric ionic liquid microspheres with high exchange capacity for fast extraction of plasmid DNA

A novel polymeric ionic liquid (PIL) microsphere, poly(1-vinyl-3-(2-methoxy-2-oxyl ethyl)imidazolium) hexafluorophosphate, is prepared via W/O emulsion polymerization. Rapid ion-exchange between the anionic moieties of PIL and DNA fragments is demonstrated facilitating the exchange equilibrium to be reached within 1 min. The PIL microspheres exhibit a high capacity of 190.7 μg mg⁻¹ for DNA adsorption. A fast DNA isolation protocol is thus developed with the PIL microspheres as solid phase adsorbent. It is feasible to facilitate DNA adsorption or stripping from the microspheres by simply regulating the concentration of salt. DNA adsorption is facilitated at low salt concentration, while higher concentration of salt entails DNA recovery from the microspheres. In practice, the retained DNA could be readily recovered with 1.0 mol L⁻¹ NaCl as stripping reagent, giving rise to a recovery of ca. 80.7%. The PIL microspheres are used for the adsorption/isolation of plasmid DNA from E. coli cell culture, demonstrating a superior adsorption performance with respect to that achieved by a commercial Plasmid Miniprep Kit.     

Polymer nanocomposites for electrical energy storage

This review highlights the frontier scientific research in the development of polymer nanocomposites for electrical energy storage applications. Considerable progress has been made over the past several years in the enhancement of the energy densities of the polymer nanocomposites via tuning the chemical structures of ceramic fillers and polymer matrix and engineering the polymer–ceramic interfaces. This article summarizes a range of current approaches to dielectric polymer nanocomposites, including the ferroelectric polymer matrix, increase of the dielectric permittivity using high‐permittivity ceramic fillers and conductive dopants, preparation of uniform composite films based on surface‐functionalized fillers, and utilization of the interfacial coupling effect. Primary attentions have been paid to the dielectric properties at different electric fields and their correlation with film morphology, chemical structure, and filler concentration. This article concludes with a discussion of scientific issues that remain to be addressed as well as recommendations for future research. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1421–1429, 2011     

Facile synthesis of graphene-supported shuttle- and urchin-like CuO for high and fast Li-ion storage

Graphene nanosheet (GNS) supported shuttle- and urchin-like CuO nanostructures are prepared by a facile low-temperature solution route. CuO nanoshuttles or urchin-like nanostructures are dispersed uniformly on GNS, forming a three dimensional CuO-GNS layer-by-layer network after stacking. When fabricated as anode materials for lithium-ion batteries, CuO-GNS composites exhibit superior Li-ion storage properties in terms of high capacity, long cycle life, and excellent rate performance. At a large current of 700 mA/g, GNS-supported CuO nanoshuttles show a higher-than-theoretical capacity of 826 mAh/g after 100 cycles, which is even larger than the reversible capacity of 771 mAh/g achieved at 70 mA/g after 40 cycles.     

MOF-derived ZnO/ZnFe2O4@RGO nanocomposites with high lithium storage performance

ZnO/ZnFe₂O₄@reduced graphene oxide (RGO) nanocomposites have been successfully synthesized through annealing treatment of Zn/Fe MOF-5@GO composites. The ZnO/ZnFe₂O₄ nanoparticles with a diameter of 12–15 nm are evenly distributed on the surface of RGO. The ZnO/ZnFe₂O₄@RGO nanocomposites show superior rate capacity and cyclic stability of 655 mAh/g after 200 cycles at 0.2 A/g for lithium ion battery (LIB) anode. The superior electrochemical property benefits from the unique structure of ZnO/ZnFe₂O₄@RGO nanocomposites, which can provide a buffer space for volume expansion, and enhance conductivity in the charge/discharge cycle.

     

Nanosize-induced hydrogen storage and capacity control in a non-hydride-forming element: rhodium

We report the first example of nanosize-induced hydrogen storage in a metal that does not absorb hydrogen in its bulk form. Rhodium particles with diameters of <10 nm were found to exhibit hydrogen-storage capability, while bulk Rh does not absorb hydrogen. Hydrogen storage was confirmed by in situ powder X-ray diffraction, solid-state (2)H NMR, and hydrogen pressure-composition isotherm measurements. The hydrogen absorption capacity could be tuned by controlling the particle size.     

Iridium-catalyzed dehydrogenation of substituted amine boranes: kinetics, thermodynamics, and implications for hydrogen storage

Dehydrogenation of amine boranes is catalyzed efficiently by the iridium pincer complex (kappa (3)-1,3-(OP ( t )Bu 2) 2C 6H 3)Ir(H) 2 ( 1). With CH 3NH 2BH 3 (MeAB) and with AB/MeAB mixtures (AB = NH 3BH 3), the rapid release of 1 equiv of H 2 is observed to yield soluble oligomeric products at rates similar to those previously reported for the dehydrogenation of AB catalyzed by 1. Delta H for the dehydrogenation of AB, MeAB, and AB/MeAB mixtures has been determined by calorimetry. The experimental heats of reaction are compared to results from computational studies.     

Amino functionalized zeolitic tetrazolate framework (ZTF) with high capacity for storage of carbon dioxide

A three dimensional -NH(2) functionalized Zeolitic Tetrazolate Framework (ZTF-1) has been reported. The framework adopts a dia topology (M-L-M angle is close to 156°). ZTF-1 shows high CO(2) (273 K) and H(2) (77 K) uptake due to the presence of the free -NH(2) group and uncoordinated tetrazolate nitrogen.     

Porous nanotube network: a novel 3-D nanostructured material with enhanced hydrogen storage capacity

A multiscale theoretical approach (ab initio and Grand Canonical Monte Carlo calculations) was used to investigate hydrogen storage in a novel three-dimensional carbon nanostructure. Our results show that a large-pore PNN can overpass the gravimetric capacity of 20% at 77 K while a Li-doped PNN can reach the value of 8% at room temperature.