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.     

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.     

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.     

Multi-criteria analysis for screening of reversible metal hydrides in hydrogen gas storage and high pressure delivery applications

Metals and alloys forming reversible hydrides with hydrogen gas are potential building blocks for compact, solid state hydrogen storage systems. Based on the materials’ thermodynamic characteristics, their use as temperature-swing gas compression and delivery systems in the hydrogen economy is also possible. Given the wide variety of materials developed and tested at laboratory and pilot scales, a harmonized method of selecting the feasible material(s) for a particular real-life application is required. This study proposes a system selection framework based on a normalized, multi-criteria metric. Using calculated values of multi-criteria metric, multi-criteria screening and ranking of potential materials has been demonstrated for a particular use case. It is found that the alloy TiMn_1.52 having value of additive metric between 0.25 and 0.35 represents the best material for a single stage system. The alloy pair CaNi₅–Ti_1.5CrMn represents the best alternative for a two-stage system with additive metric values between 0.63 and 0.82. Energy and economic characteristics of the metal hydride gas compression and delivery systems are evaluated and compared with an equivalent mechanical compression system producing the same final effect (i.e., delivery of a given quantity of gas at a defined pressure).     

Theoretical prediction of structure,electronic and optical properties of VH2 hydrogen storage material

The vanadium hydrides have better hydrogen storage capacity in comparison to the other metal hydrides. Although the structure of VH₂ hydride has been reported, the structural stability, electronic and optical properties of VH₂ hydride are unclear. To solve these problems, we apply the first-principles method to study the structural stability, electronic and optical properties of VH₂ hydrides. Similar to the metal dihydrides, four possible VH₂ hydrides such as the cubic (Fm-3m), tetragonal (I4/mmm), tetragonal (P4₂/mnm) and orthorhombic (Pnma) are designed. The result shows that the cubic VH₂ hydride is a thermodynamic and dynamical stability. In particular, the tetragonal (I4/mmm) and the orthorhombic (Pnma) VH₂ hydrides are firstly predicted. It is found that these VH₂ hydrides show metallic behavior. The electronic interaction of V (d-state)-H (s-state) is beneficial to improve the hydrogen storage in VH₂ hydride. In addition, the formation of V–H bond can improve the structural stability of VH₂ hydride. Based on the analysis of optical properties, it is found that all VH₂ hydrides show the ultraviolet response. Compared to the tetragonal and orthorhombic VH₂ hydrides, the cubic VH₂ hydride has better storage optical properties. Therefore, we believe that the VH₂ hydride is a promising hydrogen storage material.     

Porous CoNiOOH nanosheets derived from the well-mixed MOFs as stable and highly efficient electrocatalysts for water oxidation

The development of efficient and stable electrocatalysts is of great significance for improving water splitting. Among them, transition metal oxyhydroxides show excellent performance in oxygen evolution reactions (OER), but there are certain difficulties in direct preparation. Recently, Metal–organic frameworks (MOFs) as precatalysts or precursors have shown promising catalytic performance in OER and can be decomposed under alkaline conditions. Therefore, using a mild and controllable way to convert MOFs into oxyhydroxides and retaining the original structural advantages is crucial for improving the catalytic activity. Herein, a rapid electrochemical strategy is used to activate well-mixed MOFs to prepare Co/Ni oxyhydroxide nanosheets for efficient OER catalysts, and the structural transformation in this process was investigated in detail by using scanning electron microscope, X-ray diffraction, Raman, X-ray photoelectron spectroscopy and electrochemical methods. It is discovered that electrochemical activation can promote ligand substitution of well-mixed MOFs to form porous oxyhydroxide nanosheets and tune the electronic structure of the metal (Co and Ni), which can lead to more active site exposure and accelerate charge transfer. In addition, the change of structure also improves hydrophilicity, as well as benefiting from the strong synergistic effect between multiple species, the optimal a-MCoNi–MOF/NF has excellent OER performance and long-term stability. More obviously, the porous CoNiOOH nanosheets are formed in situ during electrochemical activation process through structural transformation and acts as the active centers. This work provides new insights for mild synthesis of MOFs derivatives and also provides ideas for the preparation of highly efficient catalysts.     

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.     

Commentary on “A continuous hydrogen absorption/desorption model for metal hydride reactor coupled with PCM as heat management and its application in the fuel cell power system” [Yao J,Zhu P,Guo L,Duan L,Zhang Z,Kurko S et al. Int J Hydrogen Energy 2020. https://doi.org/10.1016/j.ijhydene.2020.05.089]

A recent paper titled “A continuous hydrogen absorption/desorption model for metal hydride reactor coupled with PCM as heat management and its application in the fuel cell power system”, published in the International Journal of Hydrogen Energy, describes the desorption kinetics modification without which the authors of this paper was unable to obtain experimental dependencies in the simulation during desorption. According to the opinion of the author of this commentary, modification of the kinetics is not required, and experimental results can be obtained using the standard kinetics by replacing the inlet/outlet boundary condition with a better one.     

Synthesis and Characterization of Hetero-metallic Oxides-Reduced Graphene Oxide Nanocomposites for Photocatalytic Applications

A new AgO.CuO.WO₃/rGO nanocomposite was designed for the investigation of the degradation ability of the hybrid material under visible light irradiation. The AgO, CuO, WO₃ NPs, and AgO.CuO.WO₃ hetero-metallic oxides were fabricated via the chemical co-precipitation method. The crystallite sizes and phase analyses were investigated by recording X-ray diffraction patterns. The crystallite sizes of three metal oxides in the AgO.CuO.WO₃ hetero metal oxide were 16.7, 15.9, and 16.9 nm, respectively. The FESEM images at various magnifications were probed to study the morphology of synthesized materials. The micrographs of hetero-metallic oxides AgO.CuO.WO₃ exposed that three metal oxides merged like small particles and gives a large bulbous appearance. EDX analyses confirmed the formation of required materials with high purity. FTIR data was in agreement with the literature which facilitated to ensure the purity of synthesized samples. The optical bandgap energy was calculated via the Tauc plot indicating that the blend of three metal oxides generated a new energy level in the electronic structure is suitable for photocatalysis in the presence of visible light. The bandgap energy of hetero metallic oxides was 1.25 eV which is less than individual metal oxides signifying the tuning of the bandgap. The incorporation of rGO in AgO.CuO.WO₃ hetero-metallic oxides gives a new photocatalyst for optimum photodegradation of methylene blue in minimum time. The percentage degradation via AgO.CuO.WO₃ was 87.20% in 70 min while the percentage degradation via AgO.CuO.WO₃/rGO recorded by photocatalytic experiment was 95% in 40 min. The photocatalysis data revealed that AgO.CuO.WO₃ hetero-metallic oxides-rGO nanocomposite ensured a strong potential to uptake organic dyes from water by promoting redox reactions during photocatalysis in the minimum time limit.