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For large-scale industrial applications, it is highly desirable to create effective, economical electrocatalysts with long-term stability for the hydrogen evolution reaction (HER) at a large current density. Herein, we report a unique motif with crystalline CoFe-layered hydroxide (CoFe-LDH) nanosheets enclosed by amorphous ruthenium hydroxide (a-Ru(OH) 3 /CoFe-LDH) to realize the efficient hydrogen production at 1000 mA cm -2 , with a low overpotential of 178 mV in alkaline media. During the continuous HER process for 40 h at such a large current density, the potential remains almost constant with only slight fluctuations, indicating good long-term stability. The remarkable HER performance can be attributed to the charge redistribution caused by abundant oxygen vacancies in a-Ru(OH) 3 /CoFe-LDH. The increased electron density of states lowers the charge-transfer resistance and promotes the formation and release of H 2 molecules. The water-splitting electrolyzer with a-Ru(OH) 3 /CoFe-LDH as both an anode and a cathode in 1.0 M KOH demonstrates stable hydrogen production and a 100% faradic efficiency. The design strategy of interface engineering in this work will inspire the design of practical electrocatalysts for water splitting on an industrial scale.

The oxygen reduction reaction (ORR) is a pivotal half-reaction for full cells and metal-air batteries. However, the intrinsic sluggish kinetics of the ORR inhibits the practical applications of these environmentally friendly energy-conversion devices. Therefore, highly efficient electrocatalysts with low cost are required to promote the ORR process. Carbon materials with single-atom Fe coordinated with N and C (Fe-N-C) stand out from various non-precious electrocatalysts, and great progress of both catalysts design and mechanism understanding has been achieved in the past. In this Perspective, we start with the recent advance in design strategies of active sites in Fe-N-C and emphasize the importance of spatial configuration and electron distribution. We discuss diverse Fe-N-C species as well as their corresponding properties. At last, we give our outlook for the future development of advanced Fe-N-C electrocatalysts.

NiFe layered double hydroxides (LDHs) usually exhibit high water-dissociation ability in the alkaline media and also provide an ideal substrate for anchoring noble metals, such as platinum (Pt), due to the 2D microstructure. Appropriate regulation of the interaction between Pt and substrate could enhance the intrinsic activity of composite catalysts toward the hydrogen evolution reaction (HER) in the alkaline media. Herein, we electrodeposit Pt nanoparticles on amorphous NiFe LDH (Pt/NiFe-ED) or crystalline NiFe LDH (Pt/NiFe-HD) to regulate the interaction between Pt and NiFe LDH. Experimental results reveal that Pt nanoparticles on NiFe-ED are smaller than those on NiFe-HD and possess a narrower size distribution. Thus, Pt/NiFe-ED (300 μM) exhibits a much lower overpotential of 81 mV at 100 mA cm -2 than Pt/NiFe-HD. In contrast, Pt/NiFe-HD exhibits a higher intrinsic activity than Pt/NiFe-ED, which could be caused by the easily elongated Pt-O bond. These findings provide new opportunities to understand the relationship between activity and crystallinity of substrates in the composite electrocatalyst.

Efficient electrocatalysts for the hydrogen evolution reaction (HER) are significant for the utilization of hydrogen as a fuel, particularly under alkaline conditions. However, the sluggish kinetics of HER remains a challenge. Here we demonstrate an efficient HER catalyst comprising Ru and AgCl nanoparticles anchored on Ag nanowires (Ru/AgCl@Ag), which delivers a low overpotential of 12 mV at 10 mA cm -2 and a Tafel slope of 38 mV decade -1 . A high mass activity of 214 mA mg -1 at an overpotential of 25 mV and a long-term durability in 1.0 M KOH are observed. In combination with computational simulations, we find that the high electronegativity of chlorine in AgCl and d-band electrons from Ru synergistically destabilize the water molecule and modulate H adsorption/desorption on the surface of Ru/AgCl@Ag, respectively. This work opens a promising avenue for the facile design and application of highly active and stable composite electrocatalysts toward water splitting.

Optimizing active electronic states responding to catalysis is of paramount importance for developing high-activity catalysts because thermodynamics itself may not favor forming an optimal electronic state. Setting the monolayer transition metal dichalcogenide (TMD) ReS 2 as a model for the hydrogen evolution reaction (HER), we uncover that intrinsic charge engineering has an auto-optimizing effect on enhancing catalytic activity through regulating active electronic states. The experimental and theoretical results show that intrinsic charge compensation from S to Re-Re bonds could manipulate the active electronic states, allowing hydrogen to absorb the active sites neither strongly nor weakly. Two types of S sites exhibit the optimal hydrogen adsorption free energies (Δ G H* ) of 0.016 and 0.061 eV, which are the closest to zero corresponding to the highest HER activity. This auto-optimization via charge engineering is further demonstrated by higher turnover frequency per sulfur atom of 1-10 s -1 and lower overpotential of -147 mV at 10 mA cm -2 than those of other TMDs through multiscale activation and optimization. This work opens an avenue in designing extensive active catalysts through intrinsic charge engineering strategy.

A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 μm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C.

Homogeneous LiF/Fe/Graphene nanocomposites as cathode material for lithium ion batteries have been synthesized for the first time by a facile two-step strategy, which not only avoids the use of highly corrosive reagents and expensive precursors but also fully takes advantage of the excellent electronic conductivity of graphene. The capacity remains higher than 150 mA h g(-1) after 180 cylces, indicating high reversible capacity and stable cyclability. The ex situ XRD and HRTEM investigations on the cycled LiF/Fe/G nanocomposites confirm the formation of FeF(x) and the coexistence of LiF and FeF(x) at the charged state. Therefore, the heterostructure nanocomposites of LiF/Fe/Graphene with nano-LiF and ultrafine Fe homogeneously anchored on graphene sheets could open up a novel avenue for the application of iron fluorides as high-performance cathode materials for lithium-ion batteries.