Electrocatalytic CO2 Reduction on CuOx Nanocubes: Tracking the Evolution of Chemical State,Geometric Structure,and Catalytic Selectivity using Operando Spectroscopy

The direct electrochemical conversion of carbon dioxide (CO₂) into multi‐carbon (C₂₊) products still faces fundamental and technological challenges. While facet‐controlled and oxide‐derived Cu materials have been touted as promising catalysts, their stability has remained problematic and poorly understood. Herein we uncover changes in the chemical and morphological state of supported and unsupported Cu₂O nanocubes during operation in low‐current H‐Cells and in high‐current gas diffusion electrodes (GDEs) using neutral pH buffer conditions. While unsupported nanocubes achieved a sustained C₂₊ Faradaic efficiency of around 60 % for 40 h, the dispersion on a carbon support sharply shifted the selectivity pattern towards C₁ products. Operando XAS and time‐resolved electron microscopy revealed the degradation of the cubic shape and, in the presence of a carbon support, the formation of small Cu‐seeds during the surprisingly slow reduction of bulk Cu₂O. The initially (100)‐rich facet structure has presumably no controlling role on the catalytic selectivity, whereas the oxide‐derived generation of under‐coordinated lattice defects, can support the high C₂₊ product yields.     

Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes

The first reversible N-heterocyclic carbene (NHC) induced α-H abstraction in tungsten(VI) imido-dialkyl dialkoxide complexes is reported. Treatment of W(NAr)(CH₂Ph)₂(OtBu)₂ (Ar=2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl) with different NHCs leads to the formation of complexes of the type W(NAr)(CHPh)(NHC)(CH₂Ph)(OtBu) in excellent isolated yields of up to 96 %. The highly unusual release of the tert-butoxide ligand as tBuOH in the course of the reaction was observed. The formed alkylidene complexes and tBuOH are in an equilibrium with the NHC and the dialkyl complexes. Reaction kinetics were monitored by ¹H NMR spectroscopy. A correlation between the steric and electronic properties of the NHC and the reaction rates was observed. Kinetics of a deuterium-labeled complex in comparison to its non-deuterated counterpart revealed the presence of a strong primary kinetic isotope effect (KIE) of 4.2, indicating that α-H abstraction is the rate-determining step (RDS) of the reaction.     

Neyman smooth goodness-of-fit tests for the marginal distribution of dependent data

We establish a data-driven version of Neyman??s smooth goodness-of-fit test for the marginal distribution of observations generated by an ??-mixing discrete time stochastic process ${(X_t)_{t \in \mathbb {Z}}}$ . This is a simple extension of the test for independent data introduced by Ledwina (J Am Stat Assoc 89:1000?C1005, 1994). Our method only requires additional estimation of the cumulative autocovariance. Consistency of the test will be shown at essentially any alternative. A brief simulation study shows that the test performs reasonable especially for the case of positive dependence. Finally, we illustrate our approach by analyzing the validity of a forecasting method (??historical simulation??) for the implied volatilities of traded options.     

Rhodium-catalyzed decarboxylative cycloaddition route to substituted anilines

A convenient method for preparing substituted anilines via a Rh-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and 2-oxazolone was discovered. The initial cycloaddition adducts undergo facile decarboxylation of carbon dioxide to afford aniline products. Reaction conditions are mild, and only 3 mol % Rh catalyst is required. High regioselectivity was observed when an unsymmetrical diyne was used as a starting material.     

Properties of radiation‐modified blends of polyethylene with elastomers and liquid crystalline copolyester

The results are given on the effect of γ‐irradiation on properties of blends of high and low‐density polyethylene (HDPE, LDPE) with elastomers ‐ethylene/propylene/diene rubber (EPDM) and chlorinated polyethylene (CPE), and thermotropic liquid crystalline polymer (LCP). The morphological, thermal, mechanical properties (including thermosetting properties) and adhesion properties of blended composites were investigated. A special attention was paid to the applicability of the blends as thermosetting materials (TSM). The LCP used was a copolyester of poly(ethylene terephthalate) with p‐(hydroxybenzoic acid) in the ratio 40 : 60. It was found that addition of LCP essentially influenced the thermomechanical and adhesion properties of PE composites, irradiated up to the absorbed dose 150 kGy, as well as the dimensional stability of thermosetting products, made from polyethylene/elastomer mixtures. The results show that such ternary blends considerably improve the exploitation conditions of irradiated polyethylene and useful thermosetting materials can be obtained.     

Self-contained two-layer shallow-water theory of strong internal bores

We show that interfacial gravity waves comprising strong hydraulic jumps (bores) can be described by a two-layer hydrostatic shallow-water (SW) approximation without invoking additional front conditions. The theory is based on a new SW momentum equation which is derived in locally conservative form containing a free parameter α. This parameter, which defines the relative contribution of each layer to the pressure at the interface, affects only hydraulic jumps but not continuous waves. The Rankine–Hugoniot jump conditions for the momentum and mass conservation equations are found to be mathematically equivalent to the classical front conditions, which were previously thought to be outside the scope of SW approximation. Dimensional arguments suggest that α depends on the density ratio. For nearly equal densities, both layers are expected to affect interfacial pressure with approximately equal weight coefficients, which corresponds to $\alpha \approx 0$. The front propagation velocity for $\alpha =0$ agrees well with experimental and numerical results in a wide range of bore strengths. A remarkably better agreement with high-accuracy numerical results is achieved by $\alpha =\sqrt{5}-2$, which yields the largest height that a stable gravity current can have.