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Using seawater can reduce the dependence on freshwater resources to generate hydrogen by electrocatalytic water splitting. However, the stability and activity of hydrogen evolution reaction (HER) electrocatalysts are highly influenced by the pH of seawater. In this regard, the development of the practical application of HER depends on the creation of highly active non-noble metal electrocatalysts. Here, we propose a technique to optimize the electrocatalytic activity and stability of MoO3 by utilizing titanium felt as the substrate. We show an HER overpotential as low as 83 mV at -10 mA cm-2 in neutral pH conditions. The present results show that electrocatalysts based on earth-abundant metals can perform well in saltwater HER, especially at a near-neutral pH (pH similar to 7). In a neutral saltwater electrolyte (0.55 M PBS + 0.5 M NaCl), this electrocatalyst showed stable performance for 250 h at a constant current density of -100 mA cm-2, indicating its promising application in seawater-based hydrogen generation. Compared with noble metals, this electrocatalyst provides a cost-effective option for economic seawater hydrogen generation, promoting the potential of seawater electrolysis.

Nanofibers and nanorods of NiCo- and NiCoFe- oxides and phosphides were synthesized by hydrothermal methods, followed by phosphidation to yield (Ni,Co)P, (Ni,Co)2P, and FeP. The materials were evaluated as electrocatalysts for the oxygen evolution reaction (OER) in water splitting in the presence of a magnetic field in two electrolytes: 1 M KOH and 1 M phosphate buffer saline (PBS) solution. A standard electrochemical cell was equipped with disk magnets directed perpendicular to the electric field. The magnetic field affected the catalyst interface and increased the reaction rate. The best catalyst was found to be NiCoP, and the overpotential (at 10 mA/cm2) was reduced from 330 to 260 mV when a magnetic field of 100 mT was applied and further to 170 mV when a magnetic field of 200 mT was applied. NiCoP has the highest proportion of magnetic domains aligned due to having the highest saturation magnetization (Ms), remanence magnetization (Mr), and the lowest coercivity (Hc). The mixed transition metal phosphide catalysts were found to partly transform into (Ni,Co)3(PO4)2 during electrocatalysis; however, they still responded to a change in the magnetic field. The results show that a weak magnetic field can improve the performance of electrocatalysts based on certain transition metals in a neutral pH electrolyte mimicking seawater.

The electrochemical glucose oxidation reaction (GOR) presents an opportunity to produce hydrogen and high-value chemical products. Herein, we investigate the effect of Sn in Ni nanoparticles for the GOR to formic acid (FA). Electrochemical results show that the maximum activity is related to the amount of Ni, as Ni sites are responsible for catalyzing the GOR via the NiOOH/Ni(OH)₂ pair. However, the GOR kinetics increases with the amount of Sn, associated with an enhancement of the OH⁻ supply to the catalyst surface for Ni(OH)₂ reoxidation to NiOOH. NiSn nanoparticles supported on carbon nanotubes (NiSn/CNT) exhibit excellent current densities and direct GOR via C−C cleavage mechanism, obtaining FA with a Faradaic efficiency (FE) of 93 % at 1.45 V vs. reversible hydrogen electrode. GOR selectivity is further studied by varying the applied potential, glucose concentration, reaction time, and temperature. FE toward FA production decreases due to formic overoxidation to carbonates at low glucose concentrations and high applied potentials, while acetic and lactic acids are obtained with high selectivity at high glucose concentrations and 55 °C. Density functional theory calculations show that the SnO₂ facilitates the adsorption of glucose on the surface of Ni and promotes the formation of the catalytic active Ni³⁺ species.

Using seawater to generate green hydrogen through electrolysis is a promising strategy for energy conversion. However, direct seawater splitting to form green hydrogen suffers drawbacks from electrode corrosion due to chlorine and other impurities. Herein, we demonstrate direct electrochemical seawater splitting using a forward osmosis membrane coupled with an electrolysis cell. By using this cell, high activity (270 mV at 10 mA/cm²) and decent stability (up to 6 days) are achieved by utilizing RuO₂-(Ni,Co)₃O₄ catalyst in a neutral electrolyte. This system is further studied in various electrolytes under neutral to alkaline conditions. This proof of concept shows that seawater splitting could be coupled with semipermeable membranes, allowing for direct utilization of seawater without pretreatment or purification and evading the challenges posed by impurities.

Due to their high potential energy storage, magnetite (Fe₃O₄) nanoparticles have become appealing as anode materials in lithium-ion batteries. However, the details of the lithiation process are still not completely understood. Here, we investigate chemical lithiation in 70 nm cubic-shaped magnetite nanoparticles with varying degrees of lithiation, x = 0, 0.5, 1, and 1.5. The induced changes in the structural and magnetic properties were investigated using X-ray techniques along with electron microscopy and magnetic measurements. The results indicate that a structural transformation from spinel to rock salt phase occurs above a critical limit for the lithium concentration (x_c), which is determined to be between 0.5< x_c ≤ 1 for Fe_3−δO₄. Diffraction and magnetization measurements clearly show the formation of the antiferromagnetic LiFeO₂ phase. Upon lithiation, magnetization measurements reveal an exchange bias in the hysteresis loops with an asymmetry, which can be attributed to the formation of mosaic-like LiFeO₂ subdomains. The combined characterization techniques enabled us to unambiguously identify the phases and their distributions involved in the lithiation process. Correlating magnetic and structural properties opens the path to increasing the understanding of the processes involved in a variety of nonmagnetic applications of magnetic materials.

The magnetic properties of spinel nanoparticles can be controlled by synthesizing particles of a specific shape and size. The synthesized nanorods, nanodots and cubic nanoparticles have different crystal planes selectively exposed on the surface. The surface effects on the static magnetic properties are well documented, while their influence on spin waves dispersion is still being debated. Our ability to manipulate spin waves using surface and defect engineering in magnetic nanoparticles is the key to designing magnonic devices. We synthesized cubic and spherical nanoparticles of a classical antiferromagnetic material Co₃O₄ to study the shape and size effects on their static and dynamic magnetic proprieties. Using a combination of experimental methods, we probed the magnetic and crystal structures of our samples and directly measured spin wave dispersions using inelastic neutron scattering. We found a weak, but unquestionable, increase in exchange interactions for the cubic nanoparticles as compared to spherical nanoparticle and bulk powder reference samples. Interestingly, the exchange interactions in spherical nanoparticles have bulk-like properties, despite a ferromagnetic contribution from canted surface spins.

A manganese(II) metal-organic framework based on the hexatopic hexakis(4-carboxyphenyl)benzene, cpb6-: [Mn3(cpb)(dmf)3], was solvothermally prepared showing a Langmuir area of 438 m2/g, rapid uptake of sulfur hexafluoride (SF6) as well as electrochemical and magnetic properties, while single crystal diffraction reveals an unusual rod-MOF topology.

BACKGROUND: Sodium chlorate (NaClO3) is extensively used in the paper industry, but its production uses strictly regulated highly toxic Na2Cr2O7 to reach high hydrogen evolution reaction (HER) Faradaic efficiencies. It is therefore important to find alternatives either to replace Na2Cr2O7 or reduce its concentration.

RESULTS: The Na2Cr2O7 concentration can be significantly reduced by using Na2MoO4 as an electrolyte co-additive. Na2MoO4 in the millimolar range shifts the platinum cathode potential to less negative values due to an activating effect of cathodically deposited Mo species. It also acts as a stabilizer of the electrodeposited chromium hydroxide but has a minor effect on the HER Faradaic efficiency. X-ray photoelectron spectroscopy (XPS) results show cathodic deposition of molybdenum of different oxidation states, depending on deposition conditions. Once Na2Cr2O7 was present, molybdenum was not detected by XPS, as it is likely that only trace levels were deposited. Using electrochemical measurements and mass spectrometry we quantitatively monitored H-2 and O-2 production rates. The results indicate that 3 mu mol L-1 Na2Cr2O7 (contrary to current industrial 10-30 mmol L-1) is sufficient to enhance the HER Faradaic efficiency on platinum by 15%, and by co-adding 10 mmol L-1 Na2MoO4 the cathode is activated while avoiding detrimental O-2 generation from chemical and electrochemical reactions. Higher concentrations of Na2MoO4 led to increased oxygen production.

CONCLUSION: Careful tuning of the molybdate concentration can enhance performance of the chlorate process using chromate in the micromolar range. These insights could be also exploited in the efficient hydrogen generation by photocatalytic water splitting and in the remediation of industrial wastewater.

Through glycerol electrooxidation, we demonstrate the viability of using a PdNi catalyst electrodeposited on Ni foam to facilitate industrially relevant rates of hydrogen generation while concurrently providing valuable organic chemicals as glycerol oxidation products. This electrocatalyst, in a solution of 2 M NaOH and 1 M glycerol at 80 & DEG;C, enabled current densities above 2000 mA cm(-2) (in a voltammetric sweep) to be obtained in atmospheres of both air and N-2. Repeated potential cycling under an aerated atmosphere to these exceptional current densities indicated a high stability of the catalyst. Through steady state polarisation curves, 1000 mA cm(-2) was reached below an anodic potential of 0.8 V vs RHE. Chronoamperometry showed glycerate and lactate being the major oxidation products, with increased selectivity for lactate at the expense of glycerate in aerated systems. Aerated atmospheres were demonstrated to consistently increase the apparent Faradaic efficiency to >100%, as determined by the concentration of oxidation products in solution. The excellent performance of PdNi/Ni in aerated solutions suggests that O-2 removal from the electrolyte is not needed for an industrial glycerol electrooxidation process, and that combining electrochemical and chemical glycerol oxidation, in the presence of dissolved O-2,O- presents an important process advantage.

The development of alcohol-based electrolysis to enable the concurrent production of hydrogen with low electricity consumption still faces major challenges in terms of the maximum anodic current density achievable. Whilst noble metals enable a low electrode potential to facilitate alcohol oxidation, the deactivation of the catalyst at higher potentials makes it difficult for the obtained anodic current density to compete with water electrolysis. In this work the effect of significant parameters such as mass transport, glycerol and OH- concentration and electrolyte temperature on the glycerol electrooxidation reaction (GEOR) in alkaline conditions on a bimetallic catalyst PdNi/Ni-RDE (Pd0.9Ni0.1) has been studied to discern experimental conditions which maximise achievable anodic current density before deactivation occurs. The ratio of NaOH:glycerol in the electrolyte highly affects the rate of the GEOR. A maximum current density of 793 mA cm(-2) at-0.125 V vs. Hg/HgO through steady state polarisation curves was achieved at a moderate and intermediate rotation rate of 500 RPM in a 2 M NaOH and 1 M glycerol (ratio of 2) electrolyte at 80 & DEG;C. Shown here is a method of catalyst reactivation for enabling the longterm use of the PdNi/Ni-RDE for electrolysis at optimal conditions for extended periods of time (3 h at 300 mA cm(-2) and 10 h at 100 mA cm(-2)). Through scanning electron microscopy (SEM), X-ray photon electron spectroscopy (XPS) and X-ray diffraction (XRD) it is shown that the electrodeposition of Pd and Ni forms an alloy and that after 10 h of electrolysis the catalyst has chemical and structural stability. This study provides details on parameters significant to the maximising of the GEOR current density and the minimising of the debilitating effect that deactivation has on noble metal based electrocatalysts for the GEOR.& nbsp;(c) 2021 The Authors. Published by Elsevier Ltd.& nbsp;