Atom-economic Approach to the Synthesis of α-(Hetero)aryl-substituted Furan Derivatives from Biomass

An atom-economic ring construction approach to the synthesis of α-(hetero)arylfurans based on renewable furanic platform chemicals has been developed. Corresponding compounds have been prepared in good to excellent yields via [2+2+2] and [4+2] cycloaddition reactions using metal-catalyzed or photoredox protocols. Easily available HMF-based 2-hydroxymethyl-5-ethynylfuran and 2-hydroxymethyl-5-cyanofuran were used as starting materials. A synthetic route with an improved carbon economy factor has been implemented to achieve sustainability aim. The possible application of arylfurans as molecular conductors has been investigated by DFT calculations, which revealed excellent charge transfer properties. As a future perspective, integration of biomass processing strategy into manufacturing of molecular electronics was pointed out to achieve the aim of sustainability.     

Enhanced Physical and Mechanical Properties of Nitrile-Butadiene Rubber Composites with N-Cetylpyridinium Bromide-Carbon Black

The physical and mechanical properties of nitrile–butadiene rubber (NBR) composites with N-cetylpyridinium bromide-carbon black (CPB-CB) were investigated. Addition of 5 parts per hundred rubber (phr) of CPB-CB into NBR improved the tensile strength by 124%, vulcanization rate by 41%, shore hardness by 15%, and decreased the volumetric wear by 7% compared to those of the base rubber-CB composite.     

Polymorphs of the Gadolinite-Type Borates ZrB2O5 and HfB2O5 Under Extreme Pressure

Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO₄(OH), the behavior of the isostructural borates β-HfB₂O₅ and β-ZrB₂O₅ have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB₂O₅ features a rearrangement of the corner-sharing BO₄ tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB₂O₅ contains ten-membered rings including the rare structural motif of edge-sharing BO₄ tetrahedra with exceptionally short B−O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf⁴⁺, and tenfold coordinated Zr⁴⁺, respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs.     

Evaluation of stability of silica-supported Fe–Pd and Fe–Pt nanoparticles in aerobic conditions using thermal analysis

The applications of zerovalent iron nanoparticles (nZVI) exploit their high reactivity which decreases due to oxidation in aerobic conditions during manufacture, application, and storage. In this study, we present the new procedure for estimation of the nZVI stability to oxidation in air. The procedure is suitable for characterization of the novel materials based on the supported nZVI. Nanoscale particles were synthesized inside porous silica supports by incipient wetness impregnation with the metal precursor solutions followed by thermal treatment. The TG–DTA studies revealed the decomposition temperature of the supported precursors, as well as the interaction of Fe and precious metal precursors, which resulted in the formation of alloy nanoparticles. Characterization of the samples by XRD confirmed the formation of the nanoparticles of the metallic Pd, Pt, and Fe phases supported on SiO₂ carriers, as well as the formation of solid solutions based on the structure of precious metals. The new procedure for estimation of the nZVI stability included (1) TPR with hydrogen up to 400–425 °C followed by isothermal reduction at these temperatures; (2) in situ reoxidation with oxygen at room temperature. The samples were reduced “as obtained” and after in situ reoxidation. The results of the TPR studies exhibited that introduction of both Pd and Pt protected the Fe nanoparticles from oxidation with oxygen and air at ambient conditions.     

Anomalous High Temperature Structural Behavior of Potential Multifunctional Material SmCo0.5Cr0.5O3

Crystal structure parameters of the mixed cobaltite–chromite SmCo_0.5Cr_0.5O₃ in the temperature range of 298–1173 K were derived from in situ high-resolution X-ray synchrotron powder diffraction data. Similar to the parent SmCoO₃ compound, SmCo_0.5Cr_0.5O₃ reveals anomalous thermal expansion reflected in abnormal temperature dependence of the unit cell dimensions and the selected interatomic distances and angles. These anomalies are associated with temperature induced changes of spin state of Co³⁺ ions and coupled insulator-metal transition. Observed decreasing behavior of the bandwidth W points on the increasing population of the exited spin states of Co³⁺ ions in SmCo_0.5Cr_0.5O₃ with increasing temperature. First principle calculations revealed antiferromagnetic ground state of SmCo_0.5Cr_0.5O₃ as the most stable.     

Nitro-, Cyano-, and Methylfuroxans,and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.     

Nitride Spinel: An Ultraincompressible High‐Pressure Form of BeP2N4

Owing to its outstanding elastic properties, the nitride spinel γ‐Si₃N₄ is of considered interest for materials scientists and chemists. DFT calculations suggest that Si₃N₄‐analog beryllium phosphorus nitride BeP₂N₄ adopts the spinel structure at elevated pressures as well and shows outstanding elastic properties. Herein, we investigate phenakite‐type BeP₂N₄ by single‐crystal synchrotron X‐ray diffraction and report the phase transition into the spinel‐type phase at 47 GPa and 1800 K in a laser‐heated diamond anvil cell. The structure of spinel‐type BeP₂N₄ was refined from pressure‐dependent in situ synchrotron powder X‐ray diffraction measurements down to ambient pressure, which proves spinel‐type BeP₂N₄ a quenchable and metastable phase at ambient conditions. Its isothermal bulk modulus was determined to 325(8) GPa from equation of state, which indicates that spinel‐type BeP₂N₄ is an ultraincompressible material.     

Hierarchical Structure of NiMo Hydrodesulfurization Catalysts Determined by Ptychographic X‐Ray Computed Tomography

Hydrodesulphurization, the removal of sulphur from crude oils, is an essential catalytic process in the petroleum industry safeguarding the production of clean hydrocarbons. Sulphur removal is critical for the functionality of downstream processes and vital to the elimination of environmental pollutants. The effectiveness of such an endeavour is among other factors determined by the structural arrangement of the heterogeneous catalyst. Namely, the accessibility of the catalytically active molybdenum disulphide (MoS₂) slabs located on the surfaces of a porous alumina carrier. Here, we examined a series of pristine sulfided Mo and NiMo hydrodesulphurization catalysts of increasing metal loading prepared on commercial alumina carriers using ptychographic X‐ray computed nanotomography. Structural analysis revealed a build consisting of two interwoven support matrix elements differing in nanoporosity. With increasing metal loading, approaching that of industrial catalysts, these matrix elements exhibit a progressively dissimilar MoS₂ surface coverage as well as MoS₂ cluster formation at the matrix element boundaries. This is suggestive of metal deposition limitations and/ or catalyst activation and following prohibitive of optimal catalytic utilization. These results will allow for diffusivity calculations, a better rationale of current generation catalyst performance as well as a better distribution of the active phase in next‐generation hydrodesulphurization catalysts.     

Performance review of locking alleviation methods for continuum ANCF beam elements

Nonlinear Dynamics - The absolute nodal coordinate formulation (ANCF) is a nonlinear finite element approach proposed for the large deformation dynamics analysis of beam- and plate/shell-type...