Nickel phosphonate MOF as efficient water splitting photocatalyst

A novel microporous two-dimensional(2D)Ni-based phosphonate metal-organic framework(MOF;denoted as IEF-13)has been successfully synthesized by a simple and green hydrothermal method and fully characterized using a combination of experimental and computational techniques.Structure resolution by single-crystal X-ray diffraction reveals that IEF-13 crystallizes in the triclinic space group Pi having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand.Remarkably,this material exhibits coordinatively unsaturated nickel(II)sites,free-P0₃H₂and-P0₃H acidic groups,a C0₂accessible microporosity,and an exceptional thermal and chemical stability.Further,its in-deep optoelectronic characterization evidences a photoresponse suitable for photocatalysis.In this sense,the photocatalytic activity for challenging H₂generation and overall water splitting in absence of any co-catalyst using UV-Vis irradiation and simulated sunlight has been evaluated,constituting the first report for a phosphonate-MOF photocatalyst.IEF-13 is able to produce up to 2,200 fimol of H₂per gram using methanol as sacrificial agent,exhibiting stability,maintaining its crystal structure and allowing its recycling.Even more,170μmol of H₂per gram were produced using IEF-13 as photocatalyst in the absence of any co-catalyst for the overall water splitting,being this reaction limited by the 0₂reduction.The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.     

A note on the variance of rank-based selection strategies for genetic algorithms and genetic programming

This paper evaluates different forms of rank-based selection that are used with genetic algorithms and genetic programming. Many types of rank based selection have exactly the same expected value in terms of the sampling rate allocated to each member of the population. However, the variance associated with that sampling rate can vary depending on how selection is implemented. We examine two forms of tournament selection and compare these to linear rank-based selection using an explicit formula. Because selective pressure has a direct impact on population diversity, we also examine the interaction between selective pressure and different mutation strategies.     

Effect of photoaligning azo dye structure on liquid crystal anchoring energy

A method of controlling anchoring energy of surface interaction of liquid crystal photoaligning substances is considered to enhance the liquid crystal display performances. An important parameter of the dye's molecular structure that determines the ratio of polar and azimuthal anchoring energy is the ability to form dimers. The values of dimerization thermodynamic potentials have been found. The probability of the formation of dye molecules dimers is evaluated. The bonds conjugation transfer via intermolecular hydrogen bond is revealed, and anisotropy of polarizability of the hydrogen bond is evaluated. The effect of dimerization on polar and azimuthal anchoring energy of liquid crystal — azo dye system — is shown.     

Advanced Characterization and Optimization of NiOx:Cu-SAM Hole-Transporting Bi-Layer for 23.4% Efficient Monolithic Cu(In,Ga)Se2-Perovskite Tandem Solar Cells

The performance of five hole-transporting layers (HTLs) is investigated in both single-junction perovskite and Cu(In, Ga)Se₂ (CIGSe)-perovskite tandem solar cells: nickel oxide (NiO_x,), copper-doped nickel oxide (NiO_x:Cu), NiO_x+SAM, NiO_x:Cu+SAM, and SAM, where SAM is the [2-(3,-6Dimethoxy-9H-carbazol-9yl)ethyl]phosphonic acid (MeO-2PACz) self-assembled monolayer. The performance of the devices is correlated to the charge-carrier dynamics at the HTL/perovskite interface and the limiting factors of these HTLs are analyzed by performing time-resolved and absolute photoluminescence ((Tr)PL), transient surface photovoltage (tr-SPV), and X-ray/UV photoemission spectroscopy (XPS/UPS) measurements on indium tin oxide (ITO)/HTL/perovskite and CIGSe/HTL/perovskite stacks. A high quasi-Fermi level splitting to open-circuit (QFLS-V_oc) deficit is detected for the NiO_x-based devices, attributed to electron trapping and poor hole extraction at the NiO_x-perovskite interface and a low carrier effective lifetime in the bulk of the perovskite. Simultaneously, doping the NiO_x with 2% Cu and passivating its surface with MeO-2PACz suppresses the electron trapping, enhances the holes extraction, reduces the non-radiative interfacial recombination, and improves the band alignment. Due to this superior interfacial charge-carrier dynamics, NiO_x:Cu+SAM is found to be the most suitable HTL for the monolithic CIGSe-perovskite tandem devices, enabling a power-conversion efficiency (PCE) of 23.4%, V_oc of 1.72V, and a fill factor (FF) of 71%, while the remaining four HTLs suffer from prominent V_oc and FF losses.     

Influence of Ni and Process Parameters in Medium Mn Steels Heat Treated by High Partitioning Temperature Q&P Cycles

In this work, two medium Mn steels (5.8 and 5.7 wt pct Mn) were subjected to a quenching and partitioning (Q&P) treatment employing a partitioning temperature which corresponded to the start of austenite reverse transformation (ART). The influence of a 1.6 wt pct Ni addition in one of the steels and cycle parameters on austenite stability and mechanical properties was also studied. High contents of retained austenite were obtained in the lower quenching temperature (QT) condition, which at the same time resulted in a finer microstructure. The addition of Ni was effective in stabilizing higher contents of austenite. The partitioning of Mn and Ni from martensite into austenite was observed by TEM–EDS. The partitioning behaviour of Mn depended on the QT condition. The lower QT condition facilitated Mn enrichment of austenite laths during partitioning and stabilization of a higher content of austenite. The medium Mn steel containing Ni showed outstanding values of the product of tensile strength (TS) and total elongation (TEL) in the lower QT condition and a higher mechanical stability of the austenite.

     

Lattice damage and secondary phase formation in Yttria stabilised zirconia implanted with Fe at different temperatures

In this paper we report on the lattice damage and nanocrystalline secondary phase formation in Fe implanted Yttria stabilised zirconia (YSZ) up to a peak concentration of 10%. The implantation temperature has been varied between room temperature and 1000 °C. Samples were characterized using Rutherford backscattering/channeling and X-ray diffraction. We observed that (1) YSZ remains partially crystalline even after Fe implantation at room temperature and the lattice damage can be partially recovered if implantation is performed at elevated temperatures; (2) crystalline bcc-Fe nanoparticles have formed and grown with increasing implantation temperature. The nanoscale Fe precipitates and the YSZ matrix have a crystallographic orientation relationship.     

Phenomena at three-phase electroslag remelting

The electroslag remelting (ESR) process is widely used to produce high-quality ingots and billets for high-alloyed steels and alloys.Both the single-phase and three-phase alternating current diagram with bifilar and monofilar connection are in use for heavy ingot manufacturing.The numerical simulation of the three-phase bifilar circuit for the 120 t three-phase bifilar six-electrode ESR furnace at different variants of electric connection was presented and discussed.At the bifilar diagram of power supply,the geometrical location of electrodes in a mould holds critical importance for performances:the close location of bifilar pair electrodes provides the highest heat productivity,but the equidistant location of electrodes gives a much more uniform heat distribution.The monofilar mulit-electrode diagram of three-phase connection without phase shift shows the most uniform distribution of potential and heat generation as well as a favorable magnetic field that makes this kind the most promising for providing a high quality of heavy ingots.     

Enhanced transport properties of Sn-substituted proton-conducting BaZr0.8Sc0.2O3–δ ceramic materials

High-temperature proton conductors based on acceptor-doped barium zirconate exhibit excellent chemical stability in atmospheres containing CO₂ or H₂O. However, due to their refractory nature, these conductors have a low grain growth rate, which negatively affects the overall electrical conductivity. A possible strategy for increasing the ionic conductivity of zirconates lies in the partial substitution of Zr-ions with other isovalent dopants. In this work, we carried out systematic studies of the crystal structure, microstructure, hydration capacity, transport, and thermal properties of BaZr_0.8–xSn_xSc_0.2O_3–δ (x = 0, 0.1, and 0.2). According to X-ray powder diffraction and scanning electron microscopy data, all studied ceramic samples have a cubic perovskite structure, whose average grain size decreases with tin doping. It is found that the composition with x = 0.1 exhibits the highest values in terms of total, ionic, grain, and grain-boundary conductivities. The complex analysis of the obtained data shows that a low-level substitution of Zr⁴⁺- with Sn⁴⁺-ions is a competent approach for designing new proton-conducting electrolytes attractive for high-temperature applications.