Effects of different metal corrosion inhibitors on hydrogen suppression and film formation with Mg–Zn alloy dust in NaCl solutions

To improve the safety of wet dust removal systems for processing magnesium-based alloys, a new method is proposed for preventing hydrogen generation. In this paper, hydrogen generation by Mg–Zn alloy dust was inhibited with six common metal corrosion inhibitors. The results showed that sodium dodecylbenzene sulfonate was the best hydrogen inhibitor, while CeCl₃ enhanced hydrogen precipitation. The film-forming stability of sodium dodecylbenzene sulfonate was tested with different contents, temperatures, Cl^? concentrations and perturbation rates. The results showed that this inhibitor formed stable protective films on the surfaces of Mg–Zn alloy particles, and adsorption followed the Langmuir adsorption model.     

Metal chlorides-promoted ammonia absorption of deep eutectic solvent

Ammonia is considered as a promising hydrogen or energy carrier. Ammonia absorption or adsorption is an important aspect for both ammonia removal, storage and separation applications. To these ends, a wide range of solid and liquid sorbents have been investigated. Among these, the deep eutectic solvent (DES) is emerging as a promising class of ammonia absorbers. Herein, we report a novel type of DES, i.e., metal-containing DESs for ammonia absorption. Specifically, the NH₃ absorption capacity is enhanced by ca. 18.1–36.9% when a small amount of metal chlorides, such as MgCl₂, MnCl₂ etc., are added into a DES composed of resorcinol (Res) and ethylene glycol (EG). To our knowledge, the MgCl₂/Res/EG (0.1:1:2) DES outperforms most of the reported DESs. The excellent NH₃ absorption performances of metal–containing DESs have been attributed to the synergy of Lewis acid–base and hydrogen bonding interactions. Additionally, good reversibility and high NH₃/CO₂ selectivity are achieved over the MgCl₂/Res/EG (0.1:1:2) DES, which enables it to be a potential NH₃ absorber for further investigations.     

Cycling stability and adsorption mechanism at room temperature of the upscaled Ni-doped hierarchical carbon scaffold

Hydrogen adsorption performance and mechanism upon cycling of the upscaled Ni-doped hierarchical carbon scaffold (HCS) are investigated. Upon 22 hydrogen ad/desorption cycles (T = 25–50 °C and p (H₂) = 1–50 bar), the upscaled Ni-doped HCS shows excellent cycling stability with gravimetric capacity of up to 1.51 wt % H₂. This is due to mechanical stability of HCS and good distribution of Ni nanoparticles. Hydrogen adsorption mechanism of Ni-doped HCS upon cycling is experimentally and theoretically characterized. Besides dissociative adsorption onto the surface, hydrogen diffusion into the lattice structure of Ni is observed. The latter enhances with the number of ad/desorption cycles and alters the electron sharing mechanisms between Ni and H during adsorption.     

Nonlinearity in regulating the metal to insulator transition of ReNiO3 towards low temperature range

Among the existing material family of the correlated oxides, the rare earth nickelates (ReNiO₃) exhibit broadly adjustable metal to insulator transition (MIT) properties that enables correlated electronic applications, such as thermistors, thermochromics, and logical devices. Nevertheless, how to accurately control the critical temperature (T_MIT) of ReNiO₃ via the co-occupation of the rare-earth elements is yet worthy to be further explored. Herein, we demonstrate the non-linearity in adjusting the T_MIT of ReNiO₃ towards lower temperatures via introducing Pr co-occupation within ReNiO₃ (e.g., Pr_xNd_1-xNiO₃ and Pr_xSm_1-xNiO₃) as synthesized by KCl molten-salt assisted high oxygen pressure reaction approach. Although the T_MIT is effectively reduced via Pr substitution, it does not strictly follow a linear relationship, in particular, when there is large difference in the ionic radius of the co-occupation rare-earth elements. Furthermore, the most significant deviation in T_MIT from the expected linear relationship appears at an equal co-occupation ratio of the two different rare-earth elements, while the abruption in the variation of resistivity across T_MIT is also reduced. The present work highlights the importance to use adjacent rare-earth elements with co-occupation ratio away from 1:1 for achieving more linear adjustment in designing the metal to insulator transition properties for ReNiO₃.     

S/Se dual-doping promotes the formation of active Ni/Fe oxyhydroxide for oxygen evolution reaction of (sea)water splitting

Surface reconstruction produces metal oxyhydroxide (1OOH) active sites, and promoting surface reconstruction is essential for the design of OER electrocatalysts. In this paper, we reported that a large amount of active NiFeOOH was generated in-situ on the surface of nickel-iron sulfide selenide, thus exposing more active sites and efficiently catalyzing OER. In 1 M KOH solution, NiFeOOH(S,Se) achieves an ultra-low overpotential of 195 mV at the current density of 10 mA cm^?2, and the Tafel slope is only 31.99 mV dec^?1, showing excellent catalytic performance. When the current density is 100  mA cm^?2, the over-potential of NiFeOOH(S,Se) in KOH + seawater solution is 239 mV, which is almost equivalent to 231 mV in KOH solution. The excellent OER stability of the NiFeOOH(S,Se) catalyst in alkaline electrolytes was confirmed, and the overpotential did not change significantly after 4 days of testing in KOH + seawater solution.     

Facile fabrication of MOF-decorated nickel iron foam for highly efficient oxygen evolution

Metal-organic frameworks (MOFs) have emerged as efficient electrocatalysts due to the features of high specific surface area, rich pore structure and diversified composition. It is still challenging to synthesize self-supporting MOF-based catalysts using simple and low-cost fabrication methods. Herein, we successfully fabricated Ni-doped MIL-53(Fe) supported on nickel-iron foam (Ni-MIL-53(Fe)/NFF) as efficient electrocatalyst. A facile two-step solvothermal method without adding any metal salts was used, which can simplify the fabrication process and reduce the experimental cost. In the fabrication process, the bimetallic Ni-MIL-53(Fe)/NFF was in situ converted from an intermediate NiFe₂O₄/NFF. The obtained material exhibits outstanding electrocatalytic oxygen evolution performance with a low overpotential of 248 mV at 50 mA cm^?2, and a small Tafel slope of 46.4 mV dec^?1. This work sheds light on the simple and efficient preparation of bimetallic MOF-based material, which is promising in electrocatalysts.     

Wavelength-dependent photoactivity of ZnxCd1−xS and ZnCo2O4/ZnxCd1−xS for H2 and H2O2 production

Zinc cadmium sulfide (Zn_xCd_1?xS) is a good photocatalyst for hydrogen evolution reaction (HER), but an optimum x (x_m) at which a maximum HER rate is reached varies from one report to another. In this work, we examine the effect of light wavelength, not only for the HER to H₂ in the presence of Na₂S and Na₂SO₃, but also for oxygen reduction reaction (ORR) without addition of any sacrifices. For the HER under a 365 and 420 nm LED lamp, the x_m were 0.9 and 0.7, respectively. For the HER under a 330 and 395–515 nm cut-off xenon lamp, the x_m were 0.7 and 0.5, respectively. For the ORR under a 420 nm cut-off halogen lamp, a maximum production of H₂O₂ was observed at x = 0.3. Furthermore, after 4% ZnCo₂O₄ loading, Zn_xCd_1?xS had an increased activity and stability, either for the HER or for the ORR. Through a (photo)electrochemical measurement, it is proposed that the photocatalytic activity of Zn_xCd_1?xS is determined by its light absorptivity and electron reactivity. The improved performance of n-type Zn_xCd_1?xS by p-type ZnCo₂O₄ is due to formation of a p-n junction, promoting the HER (ORR) on Zn_xCd_1?xS, and the sulfide (water) oxidation on ZnCo₂O₄. This work highlights that Zn_xCd_1-xS is a promising photocatalyst for H₂ and H₂O₂ production, respectively.     

Ru-doped 3D porous Ni3N sphere as efficient Bi-functional electrocatalysts toward urea assisted water-splitting

Developing efficient, stable and ideal urea oxide (UOR) electrocatalyst is key to produce green hydrogen in an economical way. Herein, Ru doped three dimensional (3D) porous Ni₃N spheres, with tannic acid (TA) and urea as the carbon and nitrogen resources, is synthesized via hydrothermal and low-temperature treated process (Ru–Ni₃N@NC). The porous nanostructure of Ni₃N and the nickel foam provide abundant active sites and channel during catalytic process. Moreover, Ru doping and rich defects favor to boost the reaction kinetics by optimizing the adsorption/desorption or dissociation of intermediates and reactants. The above advantages enable Ru–Ni₃N@NC to have good bifunctional catalytic performance in alkaline media. Only 43 and 270 mV overpotentials are required for hydrogen evolution (HER) and oxygen evolution (OER) reactions to drive a current of 10 mA cm^?2. Moreover, it also showed good electrocatalytic performance in neutral and alkaline seawater electrolytes for HER with 134 mV to drive 10 mA cm^?2 and 83 mV to drive 100 mA cm^?2, respectively. Remarkably, the as-designed Ru–Ni₃N@NC also owns extraordinary catalytic activity and stability toward UOR. Moreover, using the synthesized Ru–Ni₃N@NC nanomaterial as the anode and cathode of urea assisted water decomposition, a small potential of 1.41 V was required to reach 10 mA cm^?2. It can also be powered by sustainable energy sources such as wind, solar and thermal energies. In order to make better use of the earth's abundant resources, this work provides a new way to develop multi-functional green electrocatalysts.     

Simply constructed highly dispersed cobalt nanoparticles in diverse N-doped graphitic carbon with remarkable performances for water electrolysis

Metal/carbon composite materials are highly promising electrocatalysts for water electrolysis. In this work, three composites of metal cobalt nanoparticles highly dispersed in N-doped carbon materials were facilely constructed by pyrolysis of different phenylenediamine based Schiff base-Co complexes (PDBs). Interestingly, the composites derived from PDBs based on different phenylenediamine exhibited different morphologies. The superior case is that rodlike composite catalyst was derived from o-phenylenediamine based PDBs. The obtained catalyst exhibited remarkable performances for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER), as well as overall water electrolysis. Only 172 and 289 mV of overpotentials and 1.57 V of cell voltage were exhibited at 10 mA cm^?2 for HER, OER and water splitting in 1.0 M KOH, respectively. The catalyst also displayed robust stability and high Faraday efficiency, and thus are potential high-performance catalyst for commercial water electrolysis.