Jan Peter Embs

On Demand: The Singular rht Net, an Ideal Blueprint for the Construction of a Metal–Organic Framework (MOF) Platform†

The need for tunable functional solid-state materials is ever increasing because of the growing demand to address persisting challenges in global energy issues, environmental sustainability, and others. [1] It is practical and preferable for such materials to be pre-designed and constructed to contain the desired properties and specific functionalities for a given targeted application. An emerging unique class of solid-state materials, namely metal–organic frameworks (MOFs), has the desired attributes and offers great promise to unveil superior materials for many lasting challenges [2] since desired functionality can be introduced pre- and/or post-synthesis. [3] A remarkable feature of MOFs is the ability to build periodic structures with in-built functional properties using the molecular building block (MBB) approach, which utilizes pre-selected organic and inorganic MBBs, with desired function, that are judiciously chosen to possess the proper geometry, shape, and directionality required to target given underlying nets. [4]

Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution

An extraordinarily interesting series of metal–organic framework compounds are the isostructural microporous coordination polymers [M2(dhtp)] (CPO-27–M, M–MOF-74 or M2(dobdc)) in which a high concentration of coordinatively unsaturated metal sites results in high initial heats of adsorption for a variety of adsorbents. We present here a comparative study of hydrogen gas adsorption experiments on CPO-27–Cu and –Mn, which show significant differences in their hydrogen uptake behaviours which can be attributed to the difference in interaction between hydrogen and the respective metal cation incorporated in the framework structure. Inelastic neutron scattering and neutron diffraction experiments were carried out to gain additional insight into the adsorption processes leading to the difference in hydrogen uptake behaviour by the two compounds. On the basis of the experimental results the hydrogen uptake properties of CPO-27–Cu and –Mn are compared, and finally related to the properties of the other members of the CPO-27 series. It is found that CPO-27–Cu demonstrates the lowest isosteric heat of adsorption for H2 of all the CPO-27–M materials reported to date, where M = Ni, Co, Mg, Zn, Mn, and Fe, whereas CPO-27–Mn demonstrates the second lowest. While all the previously reported CPO-27 materials show two steps in the adsorption isotherm and two distinct values corresponding to the first and second adsorption sites in the heats of adsorption, these are not observed for CPO-27–Cu. Consequently, the open metal site and the second adsorption site are energetically equivalent, and there is no preference for the hydrogen gas at the open metal centre.

Collective Ion Diffusion and Localized Single Particle Dynamics in Pyridinium-Based Ionic Liquids

Quasielastic neutron scattering with polarized neutrons allows for an experimental separation of single-particle and collective processes, as contained in the incoherent and coherent scattering contributions. This technique was used to investigate the dynamical processes in the pyridinium-based ionic liquid 1-butylpyridinium bis(trifluoromethylsulfonyl)-imide. We observed two diffusion processes with different time scales. The slower diffusional process was present in both the coherent and the incoherent contribution, meaning that this process has at least a partial collective nature. The second faster localized process is only present in the incoherent scattering contribution. We conclude that it is a true single-particle process on a shorter time scale.

Dramatic effect of pore size reduction on the dynamics of hydrogen adsorbed in metal–organic materials

The effects of pore size reduction on the dynamics of hydrogen sorption in metal–organic materials (MOMs) were elucidated by studying SIFSIX-2-Cu and its doubly interpenetrated polymorph SIFSIX-2-Cu-i by means of sorption, inelastic neutron scattering (INS), and computational modeling. SIFSIX-2-Cu-i exhibits much smaller pore sizes, which possess high H2 sorption affinity at low loadings. Experimental H2 sorption measurements revealed that the isosteric heat of adsorption (Qst) for H2 in SIFSIX-2-Cu-i is nearly two times higher than that for SIFSIX-2-Cu (8.6 vs. 4.6 kJ mol−1). The INS spectrum for H2 in SIFSIX-2-Cu-i is rather unique for a porous material, as only one broad peak appears at low energies near 6 meV, which simply increases in intensity with loading until the pores are filled. The value for this rotational transition is lower than that in most neutral metal–organic frameworks (MOFs), including those with open Cu sites (8–9 meV), which is indicative of a higher barrier to rotation and stronger interaction in the channels of SIFSIX-2-Cu-i than the open Cu sites in MOFs. Simulations of H2 sorption in SIFSIX-2-Cu-i revealed two hydrogen sorption sites in the MOM: direct interaction with the equatorial fluorine atom (site 1) and between two equatorial fluorine atoms on opposite walls (site 2). The calculated rotational energy levels and rotational barriers for the two sites in SIFSIX-2-Cu-i are in good agreement with INS data. Furthermore, the rotational barriers and binding energies for site 2 are slightly higher than that for site 1, which is consistent with INS results. The lowest calculated transition for the primary site in SIFSIX-2-Cu is also in good agreement with INS data. In addition, this transition in the non-interpenetrating material is higher than any of the sites in SIFSIX-2-Cu-i, which indicates a significantly weaker interaction with the host as a result of the larger pore size.

Hydrogen Dynamics in Lightweight Tetrahydroborates

Abstract The high hydrogen content in complex hydrides such as M[AlH4]x and M[BH4]x (M = Li, Na, K, Mg, Ca) stimulated many research activities to utilize them as hydrogen storage materials. An understanding of the dynamical properties on the molecular level is important to understand and to improve the sorption kinetics. Hydrogen dynamics in complex hydrides comprise long range translational diffusion as well as localized motions like vibrations, librations or rotations. All the different motions are characterized by their specific length- and timescales. Within this review we give an introduction to the physical properties of lightweight complex hydrides and illustrate the huge variety of dynamical phenomena on selected examples.

Cation dynamics in the pyridinium based ionic liquid 1-N-butylpyridinium bis((trifluoromethyl)sulfonyl) as seen by quasielastic neutron scattering.

Quasielastic neutron scattering (QENS) has been used to study the cation dynamics in the pyridinium based ionic liquid (IL) 1-N-butylpyridinium bis((trifluoromethyl)sulfonyl)imide (BuPy-Tf(2)N). This IL allows for a detailed investigation of the dynamics of the cations only, due to the huge incoherent scattering cross section of the cation (σ(inc)(cation) >> σ(inc)(anion)). The measured spectra can be decomposed into two Lorentzian lines, indicative of two distinct dynamic processes. The slower of these two processes is diffusive in nature, whereas the faster one can be attributed to localized motions. The temperature dependence of the diffusion coefficient of the slow process follows an Arrhenius law, with an activation energy of E(A) = 14.8 ± 0.3 kJ/mol. Furthermore, we present here results from experiments with polarized neutrons. These experiments clearly show that the slower of the two observed processes is coherent, while the faster one is incoherent in nature.

A study of out-of-plane cation dynamics in a bis-thiourea pyridinium chloride inclusion compound

The out-of-plane motion of the pyridinium cation in the bis-thiourea pyridinium chloride inclusion compound has been studied in a wide temperature range using (1)H NMR, dielectric spectroscopy and quasielastic neutron scattering. The geometry of this motion is obtained from the Q-dependence of the elastic incoherent structure factor determined from the quasielastic neutron scattering measurements. We find that the pyridinium cation performs out-of-plane reorientations around the axis passing through two opposite atoms of the ring. The correlation times as a function of temperature were measured in the three known crystallographic phases, finding a good agreement between the three techniques employed. The activation energy for this motion changes from 5 ± 1 kJ mol(-1) in the low-temperature phase to 1.2 ± 0.2 kJ mol(-1) in the intermediate and high-temperature phases.

Does a Dry Protein Undergo a Glass Transition

Bovine serum albumin (BSA) with extremely low hydration level 0.04, which is usually defined as dry, has been investigated in the temperature range between 200 and 340 K by incoherent inelastic neutron scattering using the neutron time-of-flight spectrometer FOCUS (PSI, Switzerland). Anomalous temperature behavior has been revealed for relaxational and low-frequency vibrational dynamics of BSA in the vicinity of 250 K. The mean-square atomic displacement has been shown to exhibit a change in the slope of temperature dependence near the same temperature. The presented results point out that the glass-like transition occurs in the dry protein.

Confinement Effects for Lithium Borohydride: Comparing Silica and Carbon Scaffolds

LiBH4 is a promising material for hydrogen storage and as a solid-state electrolyte for Li ion batteries. Confining LiBH4 in porous scaffolds improves its hydrogen desorption kinetics, reversibility, and Li+ conductivity, but little is known about the influence of the chemical nature of the scaffold. Here, quasielastic neutron scattering and calorimetric measurements were used to study support effects for LiBH4 confined in nanoporous silica and carbon scaffolds. Pore radii were varied from 8 Å to 20 nm, with increasing confinement effects observed with decreasing pore size. For similar pore sizes, the confinement effects were more pronounced for silica than for carbon scaffolds. The shift in the solid–solid phase transition temperature is much larger in silica than in carbon scaffolds with similar pore sizes. A LiBH4 layer near the pore walls shows profoundly different phase behavior than crystalline LiBH4. This layer thickness was 1.94 ± 0.13 nm for the silica and 1.41 ± 0.16 nm for the carbon scaffolds. Quasi-elastic neutron scattering confirmed that the fraction of LiBH4 with high hydrogen mobility is larger for the silica than for the carbon nanoscaffold. These results clearly show that in addition to the pore size the chemical nature of the scaffold also plays a significant role in determining the hydrogen mobility and interfacial layer thickness in nanoconfined metal hydrides.

Equilibrium and Nonequilibrium Behaviour of Ferrofluids - Experiments and Theory

Selected results on the spatiotemporal behaviour of equilibrium and nonequilibrium properties of ferrofluids in different magnetic fields are reviewed. They have been obtained in the project B13 Transport, response and instability behaviour of ferrofluids of the SFB 277 by experiments and by various theoretical methods ranging from purely analytical calculations to full numerical approaches.