Molybdenum-induced tuning 3d-orbital electron filling degree of CoSe_(2) for alkaline hydrogen and oxygen evolution reactions

The development of high-performance non-precious metal-based robust bifunctional electrocatalyst for both hydrogen evolution reaction(HER) and oxygen evolution reactions(OER) in alkaline media is essential for the electrochemical overall water splitting technologies. Herein, we demonstrate that the HER/OER performance of Co Se_(2)can be significantly enhanced by tuning the 3d-orbital electron filling degree through Mo doping. Both density functional theory(DFT) calculations and experimental results imply that the doping of Mo with higher proportion of the unoccupied d-orbital(P_(un)) could not only serve as the active center for water adsorption to enhance the water molecule activation, but also modulate the electronic structures of Co metal center leading to the optimized adsorption strength of*H. As expected, the obtained Mo-Co Se_(2)exhibits a remarkable bifunctional performance with overpotential of only 85 m V for HER and 245 m V for OER to achieve the current density of 10 m A/cm^(2)in alkaline media.This work will provide a valuable insight to design highly efficient bifunctional electrocatalyst towards HER and OER.

Analysis of Hydration Mechanism and Microstructure of Composite Cementitious Materials for Filling Mining

To obtain the compositions and microstructure of hydration products of cementitious material in different hydration ages and its growth law of filling strength, the optimal proportion of composite cementitious material was determined according to the chemical composition of cement clinker which was composed of the Portland cement 32.5R, CSA 42.5 sulphoaluminate cement and two gypsum（CS）. The characterization of composite cementitious materials in different hydration ages was conducted by NMR, XRD and SEM techniques. The mechanism of hydration was explored. It is shown that the compressive strength of the test block increases gradually with the increase of hydration age. The microstructure of composite cementitious material can be changed from Al-O octahedron into Al-O tetrahedron in the hydration process. The hydrated alkali alumi niumsilicate formed with Si-O tetrahedron and Al-O tetrahedron. The degree of polymerization of Si-O tetrahedron gradually increased, and the structural strength of cementitious materials continued to increase. The diffraction peak of clinker minerals gradually decreased with the extension of hydration age. The CaSO4 completely hydrated to produce Aft during hydration which resulted in high early strength of cementitious material. The early hydration product of composite cementitious materials was Aft with a needle bar structure. The main middle and last hydration products were CSH gel and CH gel with dense prismatic shape. The microscopic pore of composite cementitious material gradually decreased and improved the later strength of filling block. The strong support was provided for mined-out area.