Publications by authors named "Yakovenko A"

This study investigates the tribological properties of graphite foils (GF) with densities of 1.0, 1.3, and 1.

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Liquid porosimetry experiments reveal a peculiar trend of the intrusion pressure of water in hydrophobic Cu(3,3',5,5'-tetraethyl-4,4'-bipyrazolate) MOF. At lower temperature (T) range, the intrusion pressure (P) increases with T. For higher T values, P first reaches a maximum and then decreases.

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When harvesting grain crops and forage grasses using a two-phase method, trailed and/or mounted windrowers are usually used. After their passage, stubble remains on the field, which intensively loses soil moisture under sunlight and wind. To reduce these losses, the stubble, along with the soil, is crushed using disc harrows.

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Although coveted in applications, few materials expand when subject to compression or contract under decompression, i.e., exhibit negative compressibility.

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Fluids under extreme confinement show characteristics significantly different from those of their bulk counterpart. This work focuses on water confined within the complex cavities of highly hydrophobic metal-organic frameworks (MOFs) at high pressures. A combination of high-pressure intrusion-extrusion experiments with molecular dynamic simulations and synchrotron data reveals that supercritical transition for MOF-confined water takes place at a much lower temperature than in bulk water, ∼250 K below the reference values.

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Solid-gas reactions and powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF)Pz]Ag} and {[4-Br-3,5-(CF)Pz]Ag} supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF)Pz]Ag} under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above.

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Article Synopsis
  • Recent computational studies have identified new ternary nitrides, pointing to potential new materials, but synthesizing them is challenging due to high cohesive energies that slow down diffusion.
  • The authors successfully synthesized two new phases, calcium zirconium nitride (CaZrN) and calcium hafnium nitride (CaHfN), through solid state metathesis reactions involving calcium nitride (CaN) and metal chlorides (Zr, Hf).
  • It was found that a slight excess of CaN (about 20 mol %) is necessary to achieve the correct stoichiometry of CaN for producing the desired phases, as revealed by advanced synchrotron X-ray diffraction studies, which also helped explain the synthesis process compared to
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Article Synopsis
  • Flexible nanoporous materials, especially metal-organic frameworks (MOFs) like ZIF-8, have potential uses in sensors, catalysis, material separation, and energy storage.
  • This study examines how changing the crystallite size of ZIF-8 affects its flexibility and compressibility when subjected to hydrostatic pressure with water.
  • Results show that reducing the crystallite size to nanoscale decreases the flexibility and compressibility of ZIF-8 by approximately 25% and 15%, respectively, offering a method to fine-tune MOF flexibility without changing their chemical structure.
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An exploration of the synthetic and structural phase space of rare earth hybrid double perovskites AB'BX (A = organocation, B' = M, B = M, X = molecular bridging anion) that include X = NO and B' = alkali metal is reported, complementing earlier studies of the [MeN][KB(NO)] (B = Am, Cm, La-Nd, Sm-Lu, Y) (MeN = (CH)N) compounds. In the present efforts, the synthetic phase space of these systems is explored by varying the identity of the alkali metal ion at the B'-site. Herein, we report three new series of the form [MeN][B'B(NO)] (B = La-Nd, Sm-Gd; B' = Na, Rb, Cs).

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Hydrophobic flexible zeolitic imidazole frameworks (ZIFs) represent reference microporous materials in the area of mechanical energy storage, conversion, and dissipation via non-wetting liquid intrusion-extrusion cycle. However, some of them exhibit drawbacks such as lack of stability, high intrusion pressure, or low intrusion volume that make them non-ideal materials to consider as candidates for real applications. In this work, we face these limitations by exploiting the hybrid ZIF concept.

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Zeolitic Imidazolate Frameworks (ZIF) find application in storage and dissipation of mechanical energy. Their distinctive properties linked to their (sub)nanometer size and hydrophobicity allow for water intrusion only under high hydrostatic pressure. Here we focus on the popular ZIF-8 material investigating the intrusion mechanism in its nanoscale cages, which is the key to its rational exploitation in target applications.

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X-ray Compton spectroscopy is one of the few direct probes of the electron momentum distribution of bulk materials in ambient and operando environments. We report high-resolution inelastic x-ray scattering experiments with high momentum and energy transfer performed at a storage-ring-based high-energy x-ray light source facility using an x-ray transition-edge sensor (TES) microcalorimeter detector. The performance was compared with a silicon drift detector (SDD), an energy-resolving semiconductor detector, and Compton profiles were measured for lithium and cobalt oxide powders relevant to lithium-ion battery research.

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Pressure-induced thermal changes in solids-barocaloric effects-can be used to drive cooling cycles that offer a promising alternative to traditional vapor-compression technologies. Efficient barocaloric cooling requires materials that undergo reversible phase transitions with large entropy changes, high sensitivity to hydrostatic pressure, and minimal hysteresis, the combination of which has been challenging to achieve in existing barocaloric materials. Here, we report a new mechanism for achieving colossal barocaloric effects that leverages the large volume and conformational entropy changes of hydrocarbon order-disorder transitions within the organic bilayers of select two-dimensional metal-halide perovskites.

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Substantial improvements in cycle life, rate performance, accessible voltage, and reversible capacity are required to realize the promise of Li-ion batteries in full measure. Here, we have examined insertion electrodes of the same composition (VO) prepared according to the same electrode specifications and comprising particles with similar dimensions and geometries that differ only in terms of their atomic connectivity and crystal structure, specifically two-dimensional (2D) layered α-VO that crystallizes in an orthorhombic space group and one-dimensional (1D) tunnel-structured ζ-VO crystallized in a monoclinic space group. By using particles of similar dimensions, we have disentangled the role of specific structural motifs and atomistic diffusion pathways in affecting electrochemical performance by mapping the dynamical evolution of lithiation-induced structural modifications using ex situ scanning transmission X-ray microscopy, synchrotron X-ray diffraction measurements, and phase-field modeling.

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How molecules approach, bind at, and release from catalytic sites is key to heterogeneous catalysis, including for emerging metal-organic framework (MOF)-based catalysts. We use synchrotron X-ray scattering analysis to evaluate the dominant binding sites for reagent and product molecules in the vicinity of catalytic Ni-oxo clusters in NU-1000 with different surface functionalization under conditions approaching those used in catalysis. The locations of the reagent and product molecules within the pores can be linked to the activity for ethylene hydrogenation.

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Purification of C H from an C H /C H mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF ) Bp]Cu} has features very desirable in an olefin-paraffin separation material.

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Background And Objectives: Pancreatic neuroendocrine tumors (PNETs) represent a rare form of pancreatic cancer. Racial/ethnic disparities have been documented in pancreatic ductal adenocarcinoma, but health disparities have not been well described in patients with PNETs.

Methods: A retrospective review of patients with PNETs in the National Cancer Database was performed for 2004-2014.

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The infiltration of palladium and platinum nanoparticles (NPs) into the mesoporous metal-organic framework (MOF) CYCU-3 through chemical vapor infiltration (CVI) and incipient wetness infiltration (IWI) processes was systematically explored as a means to design novel NP@MOF composite materials for potential hydrogen storage applications. We employed a traditional CVI process and a new ″green″ IWI process using methanol for precursor infiltration and reduction under mild conditions. Transmission electron microscopy-based direct imaging techniques combined with synchrotron-based powder diffraction (SPD), energy-dispersive X-ray spectroscopy, and physisorption analysis reveal that the resulting NP@MOF composites combine key NP and MOF properties.

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Molten salts are promising reaction media candidates for the discovery of novel materials; however, they offer little control over oxidation state compared to aqueous solutions. Here, we demonstrated that when two hydroxides are mixed, their melts become fluxes with tunable solubility, which are surprisingly powerful solvents for ternary chalcogenides and offer effective paths for crystal growth to new compounds. We report that precise control of the oxidation state of Ni is achievable in mixed molten LiOH/KOH to grow single crystals of all known ternary K-Ni-S compounds.

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Zirconium-based metal-organic frameworks (Zr-MOFs) have aroused enormous interest owing to their superior stability, flexible structures, and intriguing functions. Precise control over their crystalline structures, including topological structures, porosity, composition, and conformation, constitutes an important challenge to realize the tailor-made functionalization. In this work, we developed a new Zr-MOF (PCN-625) with a topological net, which is similar to that of the well-known PCN-222 and NU-1000.

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Black phosphorus (BP) is a promising anode material in lithium-ion batteries (LIBs) owing to its high electrical conductivity and capacity. However, the huge volume change of BP during cycling induces rapid capacity fading. In addition, the unclear electrochemical mechanism of BP hinders the development of rational designs and preparation of high-performance BP-based anodes.

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Atypical hemolytic-uremic syndrome (aHUS) is a chronic systemic disease of a genetic nature, which is based on uncontrolled activation of the alternative complement pathway, leading to generalized thrombosis in the vessels of the microvasculature (complement-mediated thrombotic microangiopathy). To date, therapy with eculizumab is the most effective and pathogenetically substantiated method of treating patients with ASH. Using the example of three clinical cases of patients with a verified diagnosis of aHUS, the high efficiency and safety of the worlds first bioanalogue of eculizumab in the treatment of adult patients with aHUS (complement-mediated thrombotic microangiopathy) was demonstrated.

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Conductive metal-organic frameworks (c-MOFs) have drawn increasing attention for their outstanding performance in energy-related applications. However, the majority of reported c-MOFs are based on 2D structures. Synthetic strategies for 3D c-MOFs are under-explored, leaving unrealized functionality in both their structures and properties.

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Benzene and acetonitrile are two of the most commonly used solvents found in almost every chemical laboratory. Titan is one other place in the solar system that has large amounts of these compounds. On Titan, organic molecules are produced in the atmosphere and carried to the surface where they can mineralize.

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