Two-Dimensional Metal-Organic Frameworks with Unique Oriented Layers for Oxygen Reduction Reaction:Tailoring the Activity through Exposed Crystal Facets

As one of the most important families of porous materials,metal–organic frameworks(MOFs)have well-defined atomic structures.This provides ideal models for investigating and understanding the relationships between structures and catalytic activities at the molecular level.However,the active sites on the edges of two-dimensional(2D)MOFs have rarely been studied,as they are less exposed to the surfaces.Here,for the first time,we synthesized and observed that the 2D layers could align perpendicular to the surface of a 2D zeolitic imidazolate framework L(ZIF-L)with a leaf-like morphology.Owing to this unique orientation,the active sites on the edges of the 2D crystal structure could mostly be exposed to the surfaces.Interestingly,when another layer of ZIF-L-Co was grown heteroepitaxially onto ZIF-L-Zn(ZIF-L-Zn@ZIF-L-Co),the two layers shared a common b axis but rotated by 90°in the ac plane.This demonstrated that we could control exposed facets of the 2D MOFs.The ZIF-L-Co with more exposed edge active sites exhibited high electrocatalytic activity for oxygen reduction reaction.This work provides a new concept of designing unique oriented layers in 2D MOFs to expose more edge-active sites for efficient electrocatalysis.

Effect of the layer orientation on mechanics and energy evolution characteristics of shales under uniaxial loading

The uniaxial compression tests were conducted on the cylindrical shale specimens with bedding plane inclined at 0° and 90° to the axial loading direction, respectively. Effect of the bedding orientation on the mechanical property and energy evolution characteristics of shales was revealed. The failure mechanisms of the specimens with layers in 0° orientation showed splitting failure along weak bedding, while the specimens with layers in 90° orientation were failed by shearing sliding. The values of compressive strength, elastic modulus and shear modulus of samples at 0° were higher than those of samples at 90°and there was little difference of Poisson's ratio between samples at 0° and 90°. The analysis of the stress–strain energy and acoustic emission(AE) energy indicated that the growth rate of absorbed energy density and elastic energy density at 0° was significantly faster than that at 90°, hence their final values at 0°were relatively larger than the latter. Moreover, higher energy release was observed for specimens at 0°.The energy release and rapid growth of energy dissipation also appeared more early at 0°. The stress ratio63% was a critical point of energy distribution at which differences started to arise between samples at 0°and 90°. These results indicated that the failure of shale at 0° was more violent and devastative than the failure of shale at 90°.

Influence of layer orientation and interlayer bonding force on the mechanical behavior of shale under Brazilian test conditions

The mechanical behavior of inherently anisotropic shale rocks under Brazilian test conditions are investigated in this study based on experimental studies and numerical simulations. The effects of the weak lamination planes and interlayer bonding force of these layers on the failure strength and fracture patterns are studied systematically. Numerical simulations using particle flow code in two dimensions based on the discrete element method showed a good agreement with the experimental results in the failure strength and fracture patterns. The shale revealed strong anisotropic behavior with the failure strength perpendicular to the lamination plane greater than failure strength parallel to lamination plane. The failure strength of the different interlayer bonding force against the layer orientations changed significantly. Four types of fracture patterns were observed: curved fracture, broken-linear fracture, layeractivated fracture, and central-linear fracture. The observed fracture patterns are either or a combination of tensile and/or shear fractures. Increase in interlayer bonding strength decreased the quantity of micro cracks and this directly led to reduction in the anisotropic behavior. Overall the layer orientation and interlayer bonding force of the shale thus play a very important role in the anisotropic behavior of the shale.

Interaction of straight chain alcohol vapors with self-assembled MOF film by surface plasmon resonance sensing and imaging

Interaction of straight chain alcohol vapors with MOF-199-functionalized films was studied by SPR. The signals had linear relationships with the concentration of alcohols over a wide range from 0 to 70% （v/v） and were reversible in proportional to the chain length, with R2 all above 0.99.