Hierarchical and self-supporting honeycomb LaNi_5 alloy on nickel foam for overall water splitting in alkaline media

Ni-based metallic foams possessing large specific surfaces and open cell structures are of specific interest as catalysts or catalyst carriers for electrolysis of water.Traditional fabrication of Nickel foam limits the element modification choices to several inert transition metals only on polymer foam precursor and subsequent preparation of foam-based catalysts in aqueous solution or organic electrolyte.To expand the modification horizon,molten salt with wide electrochemical window and fast ion diffusion can achieve the reduction of highly active elements.Herein,we reported is a general and facile method to deposit directly of highly reactive element La and prepare hierarchical honeycomb LaNi_(5) alloy on Ni foam(ho-LaNi_(5)/NF).This self-supporting electrode presents excellent electrical coupling and conductivity between the Ni foam and LaNi_(5),which provides a 3D self-supported heterostructure with outstanding electrocatalytic activity and excellent durability for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).It exhibits excellent overpotential(1.86 V)comparable to commercial coupled IrO_(2)//Pt/C(1.85 V)at a high current density of 100 m A cm^(-2).This work may pave the way for fabricating novel 3D self-supported honeycomb alloy that can be applied as electrode for usage of clean energy.

A combined DFT and molecular dynamics study of U(Ⅵ)/calcite interaction in aqueous solution

Here we present a combined DFT and molecular dynamics study of uranyl(U(VI)) interaction mechanisms with the calcite(104) surface in aqueous solution. The roles of three anion ligands(CO_3^(2-), HCO_3^-,OH^-) and solvation effect in U(VI) interaction with calcite have been evaluated. According to our calculations, water adsorbed on the calcite(1 0 4) surface prefers to exist in molecular state rather than dissociative state. Energy analysis indicate that the positively charged uranyl species prefers to form surface complexes on the surface, while neutral uranyl species may bind with the surface via both surface complexing and ion exchange reactions of U(Ⅵ)→Ca(Ⅱ). In contrast, the negatively charged uranyl species prefer to interact with the surface via ion exchange reactions of U(Ⅵ) →Ca(Ⅱ), and the one with UO_2(CO_3)_2(H_2O)^(2-)as the reactant becomes the most favorable one in energy. We also found that uranyl adsorption increases the hydrophilic ability of the(104) surface to different extents, where the UO_2(CO_3)_3Ca_2 species contributes to the largest degree of energy changes(-53 kcal/mol). Our calculations proved that the(104) surface also has the ability to immobilize U(Ⅵ) via either surface complexing or ion exchange mechanisms under different pH values.

Theoretical studies on the complexation of Eu(Ⅲ) and Am(Ⅲ) with HDEHP： structure, bonding nature and stability

Separation of trivalent lanthanides(Ln(Ⅲ)) and actinides(An(Ⅲ)) is a key issue in the advanced spent nuclear fuel reprocessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes(TALSPEAK) process, the organophosphorus ligand HDEHP(di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(Ⅲ) from An(Ⅲ) with the combination of a holdback reagent in aqueous lactate buffer solution. In this work, the structural and electronic properties of Eu^(3+) and Am^(3+) complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory(DFT). It was found that HDEHP can coordinate with M(Ⅲ)(M=Eu, Am) cations in the form of hydrogen-bonded dimers HL_2^-(L=DEHP), and the metal ions prefer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(Ⅲ) complexes have higher interaction energies, the HL_2^- dimer shows comparable affinity for Eu(Ⅲ) and Am(Ⅲ) according to thermodynamic analysis, which may be attributed to the higher stabilities of Eu(Ⅲ) nonahydrate. It is expected that this work could provide insightful information on the complexation of An(Ⅲ) and Ln(Ⅲ) with HDEHP at the molecular level.