Porphyrin-based metal–organic frameworks (MOFs), exemplified by MOF-525, PCN-221, and PCN-224, are promising systems for catalysis, optoelectronics, and solar energy conversion. However, subtle differences between synthetic protocols for these three MOFs give rise to vast discrepancies in purported product outcomes and description of framework topologies. Here, based on a comprehensive synthetic and structural analysis spanning local and long-range length scales, we show that PCN-221 consists of Zr6O4(OH)4 clusters in four distinct orientations within the unit cell, rather than Zr8O6 clusters as originally published, and linker vacancies at levels of around 50%, which may form in a locally correlated manner. We propose disordered PCN-224 (dPCN-224) as a unified model to understand PCN-221, MOF-525, and PCN-224 by varying the degree of orientational cluster disorder, linker conformation and vacancies, and cluster–linker binding. Our work thus introduces a new perspective on network topology and disorder in Zr-MOFs and pinpoints the structural variables that direct their functional properties.

Relaxation spectra of molecular glass formers devoid of secondary relaxation maxima, as measured by dielectric spectroscopy (DS), nuclear magnetic resonance (NMR) relaxometry, photon correlation spectroscopy (PCS), and Fabry–Perot interferometry, are quantitatively compared in terms of the Kohlrausch stretching parameter βK. For a reliable estimate of βK, the excess wing contribution has to be included in the spectral analysis. The relaxation stretching probed by PCS and NMR varies only weakly among the liquids (βK = 0.58 ± 0.06). It is similar to that found in DS, provided that the liquid is sufficiently nonpolar (relaxation strength Δε≲6). For larger strengths, larger βKDS (narrowed relaxation spectra) are found when compared to those reported from NMR and PCS. Frequency–temperature superposition (FTS) holds for PCS and NMR. This is demonstrated by data scaling and, for the few glass formers for which results are available, by the equivalence of the susceptibilities χPCS″ωτ∝χNMR″τ∝χNMR″ω, i.e., measuring at a constant frequency is equivalent to measuring at a constant temperature or constant correlation time. In this context, a plot of the spin–lattice relaxation rate R1(T) as a function of the spin–spin relaxation rate R2(T) is suggested to reveal the stretching parameter without the need to perform frequency-dependent investigations. Dielectrically, we identify a trend of increasing deviations from FTS with increasing Δε. Depending on the technique and glass former, the relative relaxation strength of the excess wing varies, whereas its exponent appears to be method independent for a given substance. For polar liquids, we discuss possible reasons for the discrepancy between the results from PCS and NMR as compared to those from DS.

Ni-rich Li­(Ni1–x–y Co x Mn y )­O2-based cathodes still suffer from low cycling stability, which arises from capacity fading and impedance rise due to parasitic side reactions at the interface. Surface coatings have shown promising results in stabilizing the cathode surface and improving the cycling stability. However, a comprehensive understanding on the beneficial effect of the coating is still missing. In this paper, we used a solution-based technique to coat Ni-rich Li­(Ni0.70Co0.15Mn0.15)­O2 with a thin Al2O3 layer followed by post-annealing at 600 °C. Electrochemical characterization shows a drastic improvement of the cathode’s cycling stability due to the coating. After post-annealing, the cycling stability is even further improved, accompanied with its C-rate performance. Structural characterization confirms that annealing results in the formation of an amorphous Al2O3/LiAlO2 coating layer, which exhibits increased lithium-ion conductivity compared to the Al2O3 coating. More importantly, temperature-dependent impedance measurements reveal that the coatings do not affect the activation energy of the charge transport, which guarantees a sufficient electronic conductivity between the secondary NCM particles in the cathode. Thus, the Al2O3/LiAlO2 layer not only inhibits direct contact between electrode and electrolyte, preventing side reactions and stabilizes the performance, but also facilitates conductive pathways for lithium ions while preserving the electronic connectivity between cathode’s particles, leading to a low interfacial resistance and excellent rate capability. The results show the importance of providing a sufficiently high electrical conductivity accompanied with low activation energies in coating layers for both ions and electrons, which needs to be considered in design strategies for next-generation lithium-ion batteries.

Nanostructured and reusable 3d-metal catalysts that operate with high activity and selectivity in important chemical reactions are highly desirable. Here, a cobalt catalyst was developed for the synthesis of primary amines via reductive amination employing hydrogen as the reducing agent and easy-to-handle ammonia, dissolved in water, as the nitrogen source. The catalyst operates under very mild conditions (1.5 mol% catalyst loading, 50°C and 10 bar H 2 pressure) and outperforms commercially available noble metal catalysts (Pd, Pt, Ru, Rh, Ir). A broad scope and a very good functional group tolerance were observed. The key for the high activity seemed to be the used support: an N-doped amorphous carbon material with small and turbostratically disordered graphitic domains, which is microporous with a bimodal size distribution and with basic NH functionalities in the pores.

Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal–organic frameworks (MOFs) CAU‐10, Ce‐UiO‐66, and Al‐MIL‐53 of idealized composition [Al(OH)(ISO)], [Ce6O4(OH)4(BDC)6], and [Al(OH)(BDC)], respectively (ISO2−: isophthalate, BDC2−: terephthalate). Its use allowed the synthesis of Ce‐UiO‐66 on a gram scale. While CAU‐10 and Ce‐UiO‐66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al‐MIL‐53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large‐pore form over a broad temperature range (130–450 K). The stabilization of the large‐pore form of Al‐MIL‐53 was attributed to a high percentage of noncoordinating −COOH groups as determined by solid‐state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g−1 within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa).

Targeted recognition of medium sized molecules with mixed hydrogen bond units is essential for using porous materials for molecular separation, sensing and drug delivery.

Leaner burning and downsizing are two concepts pursued by engine developers to reduce fuel consumption and emissions. Both approaches lead to increasing challenges concerning ignition, as these concepts are typically associated with an increase in flow velocity and degree of turbulence as well as raised pressure at the moment of ignition. In this context, the use of miniaturized passively Q-switched laser spark plugs with pulse train ignition is considered as a promising alternative to conventional spark plugs.However, the application of these passively Q-switched laser spark plugs inevitably leads to the question of optimum pulse train parameters. For a better understanding, this study deals with improved flame formation by passively Qswitched laser pulse train ignition under engine-like conditions. The entire ignition process is investigated with a special focus on interactions of consecutive pulses. Therefore, three methods are combined: energy transfer measurements from laser pulse to plasma with high temporal and spatial resolution show the breakdown process depending on different pressures and fluid mixtures. The temperature decrease in the induced plasma is analyzed with measurement strategies for temporal high-resolved plasma spectroscopy especially adapted to passively Q-switched lasers. In combination with high-speed schlieren measurements, the changing local ignition conditions during pulse train ignition are demonstrated. The experiments show how consecutive pulses interact and contribute to the ignition in case of a gas flow. The used prototypes of laser spark plugs are provided by Robert Bosch GmbH.

The extraordinary sensitivity of 129Xe, hyperpolarized by spin-exchange optical pumping, is essential for magnetic resonance imaging and spectroscopy in life and materials sciences. However, fluctuations of the polarization over time still limit the reproducibility and quantification with which the interconnectivity of pore spaces can be analyzed. Here, we present a polarizer that not only produces a continuous stream of hyperpolarized 129Xe but also maintains stable polarization levels on the order of hours, independent of gas flow rates. The polarizer features excellent magnetization production rates of about 70 mL/h and 129Xe polarization values on the order of 40% at moderate system pressures. Key design features include a vertically oriented, large-capacity two-bodied pumping cell and a separate Rb presaturation chamber having its own temperature control, independent of the main pumping cell oven. The separate presaturation chamber allows for precise control of the Rb vapor density by restricting the Rb load and varying the temperature. The polarizer is both compact and transportablemaking it easily storableand adaptable for use in various sample environments. Time-evolved two-dimensional (2D) exchange spectra of 129Xe absorbed in the microporous metal–organic framework CAU-1-AmMe are presented to highlight the quantitative nature of the device.