Ni2P(O)–Fe2P(O)/CeOx as high effective bifunctional catalyst for overall water splitting

The development of cost-effective bifunctional catalysts with excellent performance and good stability is of great significance for overall water splitting. In this work, NiFe layered double hydroxides (LDHs) nanosheets are prepared on nickel foam by hydrothermal method, and then Ni₂P(O)–Fe₂P(O)/CeO_x nanosheets are in situ synthesized by electrodeposition and phosphating on NiFe LDHs. The obtained self-supporting Ni₂P(O)–Fe₂P(O)/CeO_x exhibit excellent catalytic performances in alkaline solution due to more active sites and fast electron transport. When the current density is 10 mA cm^?2, the overpotential of hydrogen evolution reaction and oxygen evolution reaction are 75 mV and 268 mV, respectively. In addition, driven by two Ni₂P(O)–Fe₂P(O)/CeO_x electrodes, the alkaline battery can reach 1.45 V at 10 mA cm^?2.     

Electronic regulation and core-shell hybrids engineering of palm-leaf-like NiFe/Co(PO3)2 bifunctional electrocatalyst for efficient overall water splitting

Constructing efficient and stable bifunctional electrocatalysts for overall water splitting remains a challenge because of the sluggish reaction kinetics. Herein, the core-shell hybrids composed of Co(PO₃)₂ nanorod core and NiFe alloy shell in situ grown on nickel foam (NiFe/Co(PO₃)₂@NF) are synthesized. Owing to the hierarchical palm-leaf-like structures and strong adhesion between NiFe alloys, Co(PO₃)₂ and substrates, the catalyst provides a large surface area and rapid charge transfer, which facilitates active sites exposure and conductivity enhancement. The interfacial effect in the NiFe/Co(PO₃)₂ core-shell structure modulates the electronic structure of the active sites around the boundary, thereby boosting the intrinsic activity. Benefiting from the stable structure, the durability of the catalyst is not impaired by the inevitable surface reconfiguration. The NiFe/Co(PO₃)₂@NF electrode presents a low cell voltage of 1.63 V to achieve 10 mA cm^?2 and manifests durability for up to 36 h at different current densities.     

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.     

Novel one- and two-dimensional InSbS3 semiconductors for photocatalytic water splitting: The role of edge electron states

Photocatalytic water splitting has become a promising technology to solve environmental pollution and energy shortage. Exploring stable and efficient photocatalysts are highly desired. Herein, we propose novel low-dimensional InSbS₃ semiconductors with good stability based on density functional theory. Such InSbS₃ structures could be obtained from their bulk crystal by suitable exfoliation methods. Our calculations indicate that two-dimensional (2D) and one-dimensional (1D) InSbS₃ nanostructures have moderate band gaps (2.54 and 1.97 eV, respectively) and suitable band edge alignments, which represents sufficient redox capacity for photocatalytic water splitting. 2D InSbS₃ monolayer possesses oxygen evolution reaction (OER) activity and 1D InSbS₃ single-nanochain possesses hydrogen evolution reaction (HER) activity under acidic conditions. Interestingly, two edge electron states can be introduced when the dimension of InSbS₃ is reduced from 2D to 1D and the new electron states can exist in arbitrary-width nanoribbons, which can effectively promote the process of HER. Moreover, InSbS₃ monolayer and single-nanochain also exhibit large solar-to-hydrogen efficiency, high carrier mobility, and excellent optical absorption properties, which can facilitate the process of photocatalytic reactions. Our findings can stimulate the synthesis and applications of low-dimensional InSbS₃ semiconductors for overall water splitting.     

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.     

Synthesis of bristlegrass-like Co-doped Ni2P composites on Ni foam for overall seawater splitting

Seawater is the most abundant resource on earth, so developing cost-effective, highly durable corrosion resistance and efficient electrocatalysts are crucial to enhance seawater splitting. Herein, we prepared 3D bristlegrass-like Co-doped Ni₂P (Co-Ni₂P) composites supported on Ni foam (NF) through a facile solvothermal method combined and a subsequent phosphatization treatment. Benefiting from the unique structure, Co-Ni₂P shows excellent electrocatalytic activity as an electrode material for both the hydrogen evolution reaction (HER, low overpotential of 116 mV at 50 mA cm^?2) and oxygen evolution reaction (OER, low overpotential of 266 mV at 50 mA cm^?2). Moreover, the as-prepared Co-Ni₂P composites exhibit excellent stability and corrosion resistance in an alkaline medium. Density functional theory (DFT) calculations were employed to evaluate the H1 adsorption of Co-Ni₂P, and the results proved the high catalytic activity for the HER. This study provides new materials with a unique morphology for overall water splitting.     

Fracture behavior of solid electrolyte LATP material based on micro-pillar splitting method

The NASICON type solid electrolyte LATP is a promising candidate for all-solid-state Li-ion batteries considering energy density and safety aspects. To ensure the performance and reliability of batteries, crack initiation and propagation within the electrolyte need to be suppressed, which requires knowledge of the fracture characteristics. In the current work, micro-pillar splitting was applied to determine the fracture toughness of LATP material for different grain orientations. The results are compared with data obtained using a conventional Vickers indentation fracture (VIF) approach. The fracture toughness obtained via micro-pillar splitting test is 0.89 ± 0.13 MPa?m^1/2, which is comparable to the VIF result, and grain orientation has no significant effect on the intrinsic fracture toughness. Being a brittle ceramic material, the effect of pre-existing defects on the toughness needs to be considered.     

Core–Shell Photoanodes for Photoelectrochemical Water Oxidation

Photoelectrochemical (PEC) water splitting into hydrogen and oxygen is a promising solution for the conversion and storage of solar energy. Because sluggish water oxidation is the bottleneck of water splitting, the design and preparation of an efficient photoanode is intensively investigated. Currently, all known photoanode materials suffer from at least one of the following drawbacks: ① low carriers separation efficiency; ② sluggish surface water oxidation reaction; ③ poor long-term stability; ④ insufficient water adsorption and gas desorption. Core–shell configurations can endow a photoanode with improved activity and stability by coating an overlayer that plays energetic, catalytic, and/or protective roles. The construction strategy has an important effect on the activity of a core–shell photoanode. Nonetheless, the mechanism for the improvement of performance is still ambiguous and is worthy of a closer examination. In this review, the successes and challenges of core–shell photoanodes for water oxidation, focusing on synthesis strategies as well as functionalities (facilitating carrier separation, surface reaction promotion, corrosion prevention, and bubble detachment) are explored. Finally, the perspectives of this class of materials in terms of new opportunities and efforts are discussed.     

Effect of particle grading on fracture behavior and thermal shock resistance of MgO-C refractories

Two types of MgO-C refractories with tight particle grading and non-tight particle grading were prepared according to Andreasen's continuous packing theory. Fracture behaviors were investigated using wedge splitting tests combined with digital image correlation method and acoustic emission techniques. The results indicated that MgO-C refractory with non-tight particle grading treated at 1400 ℃ had more in situ phases (e.g., AlN and MgAl₂O₄) and exhibited less brittleness than specimens with tight particle grading even though they had similar nominal tensile strengths. In contrast, specimens with non-tight particle grading had greater horizontal strain under various loading stages, reflecting their better ability to resist rupture deformation. In addition, more microcracks were initiated earlier in the pre-peak region, and more energy was consumed. The decrease in coarse particles and corresponding increase in fine powder content increased the interface between particles, benefiting for reducing the local stress concentration and improving the thermal shock resistance of refractories.     

Photoelectrochemical study on charge separation mechanisms of Bi2WO6 quantum dots decorated g-C3N4

In this paper, the Bi₂WO₆ quantum dots (QDs) decorated g-C₃N₄ nanoplates were successfully synthesized via a one-step hydrothermal method. The morphology of the Bi₂WO₆ could be tuned from regular nanoplates to quantum dots. Remarkably, the Bi₂WO₆ QDs coupled with g-C₃N₄ not only prevented the aggregation, but also decreased the size of Bi₂WO₆ QDs about 3.5 nm. Meanwhile, the charge separation mechanisms of Bi₂WO₆ QDs/g-C₃N₄ photocatalyst were investigated by electrochemical impedance spectra, Mott-Schottky and linear voltammetry scans. As a result, the photoelectrochemical (PEC) experiments provided forceful evidence for the charge separation mechanism of the Bi₂WO₆ QDs/g-C₃N₄ Z-scheme. The Z-scheme system not only accelerated the separation efficiency of charge, but also improved the ability of PEC water splitting at measured 1.23 V vs. RHE.