Theoretical Insights into the Selectivity of Nitrite Reduction to NH2OH on Single-Atom Catalysts.

Electroreduction of nitrate/nitrite to high-value-added products, including NH2OH, is an important way to achieve sustainable production of green energy. However, this electrosynthesis of NH2OH still suffers from poor selectivity due to the various competing reactions. Here, we screen out Ni-N4 and Cu-N4 catalysts for highly efficient nitrite electroreduction to NH2OH by adopting density functional theory (DFT) calculations. DFT calculations reveal that the high selectivity of Ni-N4 and Cu-N4 is ascribed to their weak adsorption of *NH2OH and *NH intermediates, thereby preventing the further reduction of NH2OH. Moreover, using *NO as a model intermediate, we studied the relationship between the 3d orbital occupancy and adsorption strength of the intermediate. It is found that Ni-N4 and Cu-N4 with fully occupied dxz, dyz, and dz2 orbitals have poor adsorption of *NO intermediate. This work provides a new route for NH2OH synthesis and offers perspectives on the crucial factors in determining the catalytic selectivity.

Heterogeneous Interface Induced the Formation of Hierarchically Hollow Carbon Microcubes against Electromagnetic Pollution.

Carbon materials with multilevel structural features are showing great potentials in electromagnetic (EM) pollution precaution. With ZIF-67 microcubes as a self-sacrificing precursor, hierarchical carbon microcubes with micro/mesoporous shells and hollow cavities have been successfully fabricated with the assistance of rigid SiO2 coating layers. It is found that the SiO2 layer can effectively counteract the inward shrinkage of organic frameworks during high-temperature pyrolysis due to intensive interfacial interaction. The obtained hollow porous carbon microcubes (HPCMCs) exhibit larger Brunauer-Emmett-Teller surface area and pore volume than porous carbon microcubes (PCMCs) directly derived from ZIF-67 microcubes. The unique microstructure is confirmed to be favorable for conductive loss and interfacial polarization, thus boosting the overall dielectric loss capability of carbon materials. Besides, hollow cavity will also promote multiple reflection of incident EM waves and intensify the dissipation of EM energy. As expected, HPCMCs harvest better microwave absorption performance, including strong reflection loss intensity and broad response bandwidth, than many traditional microporous/mesoporous carbon materials. This study provides a new strategy for the construction of hierarchical carbon materials and may inspire the design of carbon-based composites with excellent EM functions.

Hot Tensile Deformation Mechanism and Fracture Behavior of the ZW31/PMMC Laminate.

In this work, a Mg-Zn-Y (ZW31) alloy with good plasticity was introduced into 10 µm 10 vol% SiCp/AZ91 composite materials (PMMCs) via the extrusion compound method, and then the ZW31/PMMC laminate was prepared via multi-pass hot rolling. The hot deformation mechanism and elevated temperature tensile fracture mechanism of ZW31/PMMC laminates were studied using the elevated temperature tensile test. The elevated temperature deformation mechanism is influenced by the strain rate. At low strain rates, grain boundary slip is the primary elevated temperature deformation mechanism of the ZW31/PMMC laminate. However, at high strain rates, the activation of pipeline diffusion is facilitated by the particle deformation zone (PDZ) in the PMMC layer with a high dislocation density, leading to the dominance of dislocation climbing as the main mechanism for elevated temperature deformation of the laminate. Additionally, the implementation of a ZW31/PMMC laminate structure effectively inhibits the initiation and propagation of cavities and microcracks within the laminate layer along the normal direction (ND) while simultaneously blunting crack tips via lattice dislocation emission toward the ZW31 layer. Upon cracking of the PMMC layer, stress concentration occurs in the fracture area of the ZW31 layer, ultimately resulting in necking-induced detachment.