Synergistically Designed Dual Interfaces to Enhance the Electrochemical Performance of MoO2 /MoS2 in Na- and Li-Ion Batteries.

It is indispensable to develop and design high capacity, high rate performance, long cycling life, and low-cost electrodes materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Herein, MoO2 /MoS2 /C, with dual heterogeneous interfaces, is designed to induce a built-in electric field, which has been proved by experiments and theoretical calculation can accelerate electrochemical reaction kinetics and generate interfacial interactions to strengthen structural stability. The carbon foam serves as a conductive frame to assist the movement of electrons/ions, as well as forms heterogeneous interfaces with MoO2 /MoS2 through CS and CO bonds, maintaining structural integrity and enhancing electronic transport. Thanks to these unique characteristics, the MoO2 /MoS2 /C renders a significantly enhanced electrochemical performance (324 mAh g-1 at 1 A g-1 after 1000 cycles for SIB and 500 mAh g-1 at 1 A g-1 after 500 cycles for LIBs). The current work presents a simple, useful and cost-effective route to design high-quality electrodes via interfacial engineering.

Two-Dimensional High-Entropy Metal Phosphorus Trichalcogenides for Enhanced Hydrogen Evolution Reaction.

Developing earth-abundant and highly effective electrocatalysts for hydrogen evolution reaction (HER) is a prerequisite for the upcoming hydrogen energy society. Two-dimensional (2D) high-entropy metal phosphorus trichalcogenides (MPCh3) have the advantages of both near-continuous adsorption energies of high-entropy alloys (HEAs) and large specific surface area of 2D materials, which are excellent catalytic platforms. As a typical 2D high-entropy catalyst, Co0.6(VMnNiZn)0.4PS3 nanosheets with high-concentration active sites are successfully demonstrated to show enhanced HER performance: an overpotential of 65.9 mV at a current density of 10 mA cm-2 and a Tafel slope of 65.5 mV dec-1. Decent spectroscopy characterizations are combined with density function theory analyses to show the scenario for the enhancement mechanism by a high-entropy strategy. The optimized S sites on the edge and P sites on the basal plane provide more active sites for hydrogen adsorption, and the introduced Mn sites boost water dissociation during the Volmer step. Two-dimensional high-entropy MPCh3 provides an avenue for the combination of HEAs and 2D materials to enhance the HER performance, which also provides an alternative materials platform to explore and design superior catalysts for various electrochemical systems.

Phase-Junction Electrocatalysts towards Enhanced Hydrogen Evolution Reaction in Alkaline Media.

To ensure sustainable hydrogen production by water electrolysis, robust, earth-abundant, and high-efficient electrocatalysts are required. Constructing a hybrid system could lead to further improvement in electrocatalytic activity. Interface engineering in composite catalysts is thus critical to determine the performance, and the phase-junction interface should improve the catalytic activity. Here, we show that nickel diphosphide phase junction (c-NiP2 /m-NiP2 ) is an effective electrocatalyst for hydrogen production in alkaline media. The overpotential (at 10 mA cm-2 ) for NiP2 -650 (c/m) in alkaline media could be significantly reduced by 26 % and 96 % compared with c-NiP2 and m-NiP2 , respectively. The enhancement of catalytic activity should be attributed to the strong water dissociation ability and the rearrangement of electrons around the phase junction, which markedly improved the Volmer step and benefited the reduction process of adsorbed protons.

2D Transition Metal Dichalcogenides: Design, Modulation, and Challenges in Electrocatalysis.

Hydrogen has been deemed as an ideal substitute fuel to fossil energy because of its renewability and the highest energy density among all chemical fuels. One of the most economical, ecofriendly, and high-performance ways of hydrogen production is electrochemical water splitting. Recently, 2D transition metal dichalcogenides (also known as 2D TMDs) showed their utilization potentiality as cost-effective hydrogen evolution reaction (HER) catalysts in water electrolysis. Herein, recent representative research efforts and systematic progress made in 2D TMDs are reviewed, and future opportunities and challenges are discussed. Furthermore, general methods of synthesizing 2D TMDs materials are introduced in detail and the advantages and disadvantages for some specific methods are provided. This explanation includes several important regulation strategies of creating more active sites, heteroatoms doping, phase engineering, construction of heterostructures, and synergistic modulation which are capable of optimizing the electrical conductivity, exposure to the catalytic active sites, and reaction energy barrier of the electrode material to boost the HER kinetics. In the last section, the current obstacles and future chances for the development of 2D TMDs electrocatalysts are proposed to provide insight into and valuable guidelines for fabricating effective HER electrocatalysts.

Dual-Enhanced Doping in ReSe2 for Efficiently Photoenhanced Hydrogen Evolution Reaction.

Rhenium dichalcogenides (ReX2, X = S or Se) are catalysts that have great promise for the photoenhanced hydrogen evolution reaction (PE-HER) because of their unique physiochemical properties. However, the catalytic performance is still restricted by their low concentration of electrocatalytic activity sites and poor injection of hot electrons. Herein, dual-enhancement in ReSe2 nanosheets (NSs) with high concentration of active sites and efficient use of hot electrons is simultaneously achieved with moderate Mo doping. Contributions from exposed catalytically active sites, improved electrical conductivity, and enhanced solar spectral response are systematically investigated. Superior PE-HER catalytical performance is obtained in Re0.94Mo0.06Se2, which has more catalytically active sites and optimized band structure than other Re1- x Mo x Se2 samples. Here, it is demonstrated that only doping can reduce the overpotential (η10) from 239 to 174 mV at -10 mA cm-2 (Δ1η10 = 65 mV). Then, η10 is further improved to 137 mV under simulated AM 1.5 sun illumination (Δ2η10 = 37 mV). The total improvement (Δη10) toward PE-HER is 102 mV (Δ1η10 + Δ2η10 = 102 mV) in optimal Re0.94Mo0.06Se2. This work presents a new perspective for researching high-efficiency photoenhanced HER ReSe2-based electrocatalysts and other layered transition metal dichalcogenides.

Ruthenium Incorporated Cobalt Phosphide Nanocubes Derived From a Prussian Blue Analog for Enhanced Hydrogen Evolution.

Electrochemical water splitting in alkaline media plays an important role in mass production of hydrogen. Ruthenium (Ru), as the cheapest member of platinum-group metals, has attracted much attention, and the incorporation of trace amount of Ru with cobalt phosphide could significantly improve the hydrogen evolution reaction (HER) catalytic activity. In this work, ruthenium-incorporated cobalt phosphide nanocubes are synthesized via a reaction between Co-Co Prussian blue analog (Co-PBA) and ruthenium chloride (RuCl3) followed by the phosphidation. The sample with a Ru content of ~2.04 wt.% exhibits the best HER catalytic activity with a low overpotential of 51 and 155 mV, to achieve the current densities of -10 and -100 mA cm-2, respectively, and the Tafel slope of 53.8 mV dec-1, which is comparable to the commercial Pt/C. This study provides a new perspective to the design and construction of high performance electrocatalysts for HER and other catalytic applications in a relatively low price.

Significantly enhanced mechanical properties in AlN helix.

To safely and reliably use aluminum nitride (AlN) helices in the fabrication of novel micro/nanodevices, it is very important to know their mechanical properties. Herein, we investigate the mechanical properties of individual AlN helices using an in situ tensile-bending test. Tensile tests reveal that an AlN helix has an average ε of ∼4.7 ± 0.8% elastic deformation before a typical brittle fracture occurs. The bending test shows a two-step mechanical feature-linear-elastic followed by an elastic-plastic process-with an average ε bent of ∼54.5 ± 0.6%. Our results provide direct cognition about the mechanical properties of AlN helices and their benefit to the design of AlN-based flexible micro/nanodevices.

Synergistic Phase and Disorder Engineering in 1T-MoSe2 Nanosheets for Enhanced Hydrogen-Evolution Reaction.

MoSe2 is a promising earth-abundant electrocatalyst for the hydrogen-evolution reaction (HER), even though it has received much less attention among the layered dichalcogenide (MX2 ) materials than MoS2 so far. Here, a novel hydrothermal-synthesis strategy is presented to achieve simultaneous and synergistic modulation of crystal phase and disorder in partially crystallized 1T-MoSe2 nanosheets to dramatically enhance their HER catalytic activity. Careful structural characterization and defect characterization using positron annihilation lifetime spectroscopy correlated with electrochemical measurements show that the formation of the 1T phase under a large excess of the NaBH4 reductant during synthesis can effectively improve the intrinsic activity and conductivity, and the disordered structure from a lower reaction temperature can provide abundant unsaturated defects as active sites. Such synergistic effects lead to superior HER catalytic activity with an overpotential of 152 mV versus reversible hydrogen electrode (RHE) for the electrocatalytic current density of j = -10 mA cm-2 , and a Tafel slope of 52 mV dec-1 . This work paves a new pathway for improving the catalytic activity of MoSe2 and generally MX2 -based electrocatalysts via a synergistic modulation strategy.