In‐situ Electrochemical X‐ray Diffraction: A Rigorous Method to Navigate within Phase Diagrams Reveals β‐Fe1+xSe as Superconductor for All x

We report the precise postsynthetic control of the composition of β‐Fe_1+xSe by electrochemistry with simultaneous tracking of the associated structural changes via in situ synchrotron X‐ray diffraction. We access the full phase width of 0.01<x<0.04 and identify the superconducting state below 8 K, which in contrast to earlier reports is independent of the composition. However, in a second set of in situ X‐ray diffraction experiments, we demonstrate that β‐Fe_1+xSe forms a new phase in the presence of oxygen above a 100 °C which has the same anti‐PbO type structure but is not superconducting down to 1.8 K. The latter process can be reversed electrochemically to reinstate the superconducting state. These observations exploit the exquisite control afforded by electrochemistry in contrast with classical approaches of chemical synthesis.     

Solvent-Free Synthesis of Nano Zirconium Phenylphosphonates with Molten Phenylphosphonic Acid

Nanosized α-zirconium phenylphosphonate particles were successfully prepared by the reaction between different zirconium sources and molten phenylphosphonic acid in the absence of solvent. The resultant nanoplates exhibit particle sizes in the range of 15 to 30 nm. The use of a topotactic anion exchange method starting from α-zirconium phosphate instead resulted in the generation of 15 to 180 nm plates, while also resulting in nanoparticles with a higher degree of crystallinity. The topotactic anion exchange of the phosphate groups by phenylphosphonate groups could be performed to completion when performed in molten phenylphosphonic acid. Characterization of both the final products as well as the individual steps in the anion exchange were performed by powder XRD, fast neutron activation analysis, TGA, FTIR spectroscopy, TEM, solid-state NMR and XPS.     

Experimental Confirmation of a Predicted Porous Hydrogen-Bonded Organic Framework

Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm⁻³ and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m² g⁻¹, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.     

Inherent Ethyl Acetate Selectivity in a Trianglimine Molecular Solid

Ethyl acetate is an important chemical raw material and solvent. It is also a key volatile organic compound in the brewing industry and a marker for lung cancer. Materials that are highly selective toward ethyl acetate are needed for its separation and detection. Here, we report a trianglimine macrocycle ( TAMC ) that selectively adsorbs ethyl acetate by forming a solvate. Crystal structure prediction showed this to be the lowest energy solvate structure available. This solvate leaves a metastable, “templated” cavity after solvent removal. Adsorption and breakthrough experiments confirmed that TAMC has adequate adsorption kinetics to separate ethyl acetate from azeotropic mixtures with ethanol, which is a challenging and energy-intensive industrial separation.     

Wet-Chemically Prepared Porphyrin Layers on Rutile TiO2(110)

Porphyrins are large organic molecules that are interesting for different applications, such as photovoltaic cells, gas sensors, or in catalysis. For many of these applications, the interactions between adsorbed molecules and surfaces play a crucial role. Studies of porphyrins on surfaces typically fall into one of two groups: (1) evaporation onto well-defined single-crystal surfaces under well-controlled ultrahigh vacuum conditions or (2) more application-oriented wet chemical deposition onto less well-defined high surface area surfaces under ambient conditions. In this study, we will investigate the wet chemical deposition of 5-(monocarboxyphenyl)-10,15,20-triphenylporphyrin (MCTPP) on well-defined rutile TiO₂(110) single crystals under ambient conditions. Prior to deposition, the TiO₂(110) crystals were also cleaned wet-chemically under ambient conditions, meaning none of the preparation steps were done in ultrahigh vacuum. However, after each preparation step, the surfaces were characterized in ultrahigh vacuum with X-ray photoelectron spectroscopy (XPS) and the result was compared with porphyrin layers prepared in ultrahigh vacuum (UHV) by evaporation. The differences of both preparations when exposed to zinc ion solutions will also be discussed.     

Exit cycling for the Van der Pol oscillator and quasipotential calculations

We discuss the phenomenon of cycling for noise induced escape to a unstable periodic orbit. The presence of cycling is shown to follow from qualitative properties of two quasipotential functions. A method of numerically evaluating these quasipotential functions is described, and applied to the Van der Pol oscillator as an example. Figures resulting from these calculations reveal that nonconvergent cycling of exit measures does occur for the Van der Pol example.     

Time resolved measurements of the flow generated by suction feeding fish

The majority of aquatic vertebrates are suction feeders: by rapidly expanding the mouth cavity they generate a fluid flow outside of their head in order to draw prey into their mouth. In addition to the biological relevance, the generated flow field is interesting fluid mechanically as it incorporates high velocities, is localized in front of the mouth, and is unsteady, typically lasting between 10 and 50 ms. Using manometry and high-speed particle image velocimetry, this is the first study to quantify pressure within and outside the mouth of a feeding fish while simultaneously measuring the velocity field outside the mouth. Measurements with a high temporal (2 ms) and spatial (<1 mm) resolution were made for several feeding events of a single largemouth bass (Micropterus salmoides). General properties of the flow were evaluated, including the transient velocity field, its relationship to pressure within the mouth and pressure at the prey. We find that throughout the feeding event a relationship exists for the magnitude of fluid speed as a function of distance from the predator mouth that is based on scaling the velocity field according to the size of the mouth opening and the magnitude of fluid speed at the mouth. The velocity field is concentrated within an area extending approximately one mouth diameter from the fish and the generated pressure field is even more local to the mouth aperture. Although peak suction pressures measured inside the mouth were slightly larger than those that were predicted using the equations of motion, we find that these equations give a very accurate prediction of the timing of peak pressure, so long as the unsteady nature of the flow is included.     

Modulation versus Templating: Fine‐Tuning of Hierarchally Porous PCN‐250 Using Fatty Acids To Engineer Guest Adsorption

Modulation and templating are two synthetic techniques that have garnered significant attention over the last several years for the preparation of hierarchically porous metal–organic frameworks (HP‐MOFs). In this study, by using fatty acids with different lengths and concentrations as dual‐functional modulators/templates, we were able to obtain HP‐MOFs with tunable mesopores that exhibit different pore diameters and locations. We found that the length and concentration of the fatty acids can determine if micelle formation occurs, which in turn dictates the porosity of the resulting HP‐MOFs. The HP‐MOFs with different mesopores differed in their performance in gas uptake and dye adsorption, and the structure–performance relationships were ascribed to the pore diameters and locations. This approach could provide a potentially universal method to efficiently introduce hierarchal mesopores into existing microporous MOF adsorbents with tunable properties.     

Photoinduced Nonlinear Contraction Behavior in Metal–Organic Frameworks

The photoinduced dynamic behavior of flexible materials has received considerable attention for potential applications, such as in data storage or as smart optical devices and molecular mechanical actuators. Until now, precisely controlling expansion and contraction with light has remained a challenge. Unraveling the detailed mechanisms of photoinduced structural transformations remains a critical step necessary to understand the molecular architecture necessary for the design of sensitive photomechanical actuators. Herein, a two-dimensional flexible metal–organic framework [Zn₂(bdc)₂(3-CH₃-spy)₂]⋅H₂O ( Zn₂-1 ; H₂bdc=1,4-benzenedicaboxylic acid; 3-CH₃-spy=3-methylstyrylpyridine) with a positive volumetric thermal expansion coefficient of +78.78×10⁻⁶ K⁻¹ is reported. Upon light irradiation at different wavelengths, the MOF underwent a [2+2] cycloaddition, which afforded a family of isomeric, three-dimensional MOFs ( Zn₂-2 n , n=a–d) in a single-crystal-to-single-crystal (SCSC) manner. An unprecedented phenomenon, that is, photoinduced nonlinear contraction (PINC), was observed during this conversion. The PINC is caused by conformational changes in the 3-CH₃-spy and bdc²⁻ ligands, the bending of metal–ligand bonds, and the local distortion of the paddle-wheel SBUs. The formation of a “wrinkle morphology” on the crystal surface after the photoreaction was observed by AFM. This PINC behavior can broaden the studies on materials expansion and offer a photodriven approach for the future design of supersensitive photomechanical actuators.