Engineering hierarchical NiFe-layered double hydroxides derived phosphosulfide for high-efficiency hydrogen evolving electrocatalysis

Exploring robust, highly efficient, and cost-effective non-noble metal electrocatalysts for replacing Pt in hydrogen evolution reaction (HER) is of great significance. In this study, we skillfully synthesized binary transition-metal (i.e., nickel and iron) phosphosulfides on nickel foam (NiFeSP/NF) via a sulfuration/phosphorization treatment of bimetallic layered double hydroxides (LDH). Taking the advantage of the presence of active heterointerfaces among Ni₂P, Ni₃S₂, and FeS₂, the NiFeSP/NF catalyst, which was advantageous of the highly exposed active sites, exhibited an extraordinary catalytic activity in HER—an overpotential of 70 mV at a current density of 10 mA cm⁻² and a Tafel slope of 69 mV dec⁻¹, outperforming most of the existing counterparts. Moreover, NiFeSP/NF catalysts demonstrated favorable long-term catalytic stability for 10 h. We contributed this superior catalytic activity to the characteristic attributes of NiFeSP/NF, which could be stemmed from its exquisite catalyst design: (i) the co-occurrence of highly HER-favored crystalline Ni₂P, Ni₃S₂, and FeS₂ in bimetallic phosphosulfides and (ii) the existence of multi-functional phase interfaces among Ni₂P, Ni₃S₂, and FeS₂ in the NiFeSP/NF hierarchical structure. The present study exemplified an effective strategy for designing HER-favored bimetallic phosphosulfides and provided the scientific base for the insight into the catalytic nature of multi-metallic phosphosulfides.     

Syntheses,structures and magnetic property of two copper complexes with cyclic dimer and 2D herringbone-like network built from helical motif

Two copper(II) complexes, Cu₂{3,5-(NO₂)₂sal}₂(2,2′-bipy)₂ · 0.5H₂O (1) and [Cu₂{3,5-(NO₂)₂sal}₂(4,4′-bipy)(H₂O)₂]_n (2) (3,5-(NO₂)₂sal = 3,5-dinitrosalicylate, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), were synthesized by hydrothermal reactions and characterized by single crystal X-ray analysis. There are discrete cyclic binuclear structure in 1 and 2D herringbone-like network structure in 2, although bridging ligand 3,5-(NO₂)₂sal in 1 and 2 has same coordination model. Variable temperature magnetic measurement reveals small ferromagnetic interactions in complex 1.     

Low temperature selective catalytic reduction of NOx with NH3 over amorphous MnOx catalysts prepared by three methods

Unsupported manganese oxide catalysts with amorphous phase were prepared by three methods, and their activities for SCR of NO_x with ammonia were investigated in the presence of O₂. The results showed the catalysts have superior low temperature activity, and the NO_x conversion is about 98% at 80 °C, and nearly 100% NO_x conversion between 100 and 150 °C. Due to competing adsorption with the reactant, H₂O has slight impact on the activity. The activity was suppressed with coexisting of SO₂, however the deactivation of SO₂ is reversible. The excellent low temperature catalytic activity of amorphous MnO_x catalysts is mainly due to their amorphous phase and high specific areas.     

Transparent YAG obtained by spark plasma sintering of co-precipitated powder. Influence of dispersion route and sintering parameters on optical and microstructural characteristics

A fine-grained (330 nm) yttrium aluminium garnet (YAG) ceramic, presenting a non-negligible transparency (66% RIT at 600 nm), was obtained by spark plasma sintering. The YAG powder was manufactured by co-precipitation, starting from a yttrium and aluminium chlorides solution. A soft precursor was obtained, whose phase evolution was studied by X-ray diffraction. Calcined powders were dispersed by either ball milling or by ultrasonication and then subjected to spark plasma sintering at several temperatures (1200–1400 °C) and for a reduced time (15 min). It is shown that the dispersion method plays a key role in enhancing the optical characteristics of YAG ceramics, in order to obtain a material with a small grain size, transparent in both the visible and the infrared range.     

Graphdiyne as a promising substrate for stabilizing Pt nanoparticle catalyst

At present, Pt nanoparticle catalysts in fuel cells suffer from aggregation and loss of chemical activity. In this work, graphdiyne, which has natural porous structure, was proposed as substrate with high adsorption ability to stabilize Pt nanoparticles. Using multiscale calculations by ab initio method and the ReaxFF potential, geometry optimizations, molecular dynamics simulations, Metropolis Monte Carlo simulations and minimum energy paths calculations were performed to investigate the adsorption energy and the rates of desorption and migration of Pt nanoparticles on graphdiyne and graphene. According to the comparison between graphdiyne and graphene, it was found that the high adsorption ability of graphdiyne can avoid Pt nanoparticle migration and aggregation on substrate. Then, simulations indicated the potential catalytic ability of graphdiyne-Pt-nanoparticle system to the oxygen reduction reaction in fuel cells. In summary, graphdiyne should be an excellent material to replace graphite or amorphous carbon matrix for stabilizing Pt nanoparticle catalysts.     

Nb2O5 hollow nanospheres as anode material for enhanced performance in lithium ion batteries

Nb₂O₅ hollow nanospheres of average diameter ca. ～29 nm and hollow cavity size ca. 17 nm were synthesized using polymeric micelles with core–shell–corona architecture under mild conditions. The hollow particles were thoroughly characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermal (TG/DTA) and nitrogen adsorption analyses. Thus obtained Nb₂O₅ hollow nanospheres were investigated as anode materials for lithium ion rechargeable batteries for the first time. The nanostructured electrode delivers high capacity of 172 mAh g^?1 after 250 cycles of charge/discharge at a rate of 0.5 C. More importantly, the hollow particles based electrodes maintains the structural integrity and excellent cycling stability even after exposing to high current density 6.25 A g^?1. The enhanced electrochemical behavior is ascribed to hollow cavity coupled with nanosized Nb₂O₅ shell domain that facilitates fast lithium intercalation/deintercalation kinetics.     

Influence of powder physicochemical characteristics on microstructural and optical aspects of YAG and Er:YAG ceramics obtained by SPS

The present work aims to establish a correlation between the characteristics of YAG and Er:YAG commercial powders produced by two different synthesis routes and sintered ceramic microstructures and their optical aspect by taking into account the influence of pressure applied during the Spark Plasma Sintering (SPS) process. Physical and chemical characteristics of the powders were compared using various techniques such as SEM, XRD, laser diffraction and chemical analyses. Their behaviours were evaluated through a rheological study, compressibility tests and dilatometry cycles using SPS. This paper pinpoints the most important powder features which influence the optical quality of YAG and Er:YAG ceramics. The optical quality is mainly affected by the porosity, related to powder characteristics that affect particle rearrangement, densification and grain growth. The applied pressure induces microstructural heterogeneities depending on the starting material used and resulting in core-shell aspects of sintered ceramics.     

Synergy-Compensation Effect of Ferroelectric Polarization and Cationic Vacancy Collaboratively Promoting CO2 Photoreduction

Photocatalytic CO₂ reduction is severely limited by the rapid recombination of photo-generated charges and insufficient reactive sites. Creating electric field and defects are effective strategies to inhibit charge recombination and enrich catalytic sites, respectively. Herein, a coupled strategy of ferroelectric poling and cationic vacancy is developed to achieve high-performance CO₂ photoreduction on ferroelectric Bi₂MoO₆, and their interesting synergy-compensation relationship is first disclosed. Corona poling increases the remnant polarization of Bi₂MoO₆ to enhance the intrinsic electric field for promoting charge separation, while it decreases the CO₂ adsorption. The introduced Mo vacancy (V_Mo) facilitates the adsorption and activation of CO₂, and surface charge separation by creating local electric field. Unfortunately, V_Mo largely reduces the remnant polarization intensity. Coupling poling and V_Mo not only integrate their advantages, resulting in an approximately sevenfold increased surface charge transfer efficiency, but also compensate for their shortcomings, for example, V_Mo largely alleviates the negative effects of ferroelectric poling on CO₂ adsorption. In the absence of co-catalyst or sacrificial agent, the poled Bi₂MoO₆ with V_Mo exhibits a superior CO₂-to-CO evolution rate of 19.75 µmol g⁻¹ h⁻¹, ≈8.4 times higher than the Bi₂MoO₆ nanosheets. This work provides new ideas for exploring the role of polarization and defects in photocatalysis.