Unraveling the Role of the Stoichiometry of Atomic Layer Deposited Nickel Cobalt Oxides on the Oxygen Evolution Reaction.

Nickel cobalt oxides (NCOs) are promising, non-precious oxygen evolution reaction (OER) electrocatalysts. However, the stoichiometry-dependent electrochemical behavior makes it crucial to understand the structure-OER relationship. In this work, NCO thin film model systems are prepared using atomic layer deposition. In-depth film characterization shows the phase transition from Ni-rich rock-salt films to Co-rich spinel films. Electrochemical analysis in 1 m KOH reveals a synergistic effect between Co and Ni with optimal performance for the 30 at.% Co film after 500 CV cycles. Electrochemical activation correlates with film composition, specifically increasing activation is observed for more Ni-rich films as its bulk transitions to the active (oxy)hydroxide phase. In parallel to this transition, the electrochemical surface area (ECSA) increases up to a factor 8. Using an original approach, the changes in ECSA are decoupled from intrinsic OER activity, leading to the conclusion that 70 at.% Co spinel phase NCO films are intrinsically the most active. The studies point to a chemical composition dependent OER mechanism: Co-rich spinel films show instantly high activities, while the more sustainable Ni-rich rock-salt films require extended activation to increase the ECSA and OER performance. The results highlight the added value of working with model systems to disclose structure-performance mechanisms.

Direct Hybridization of Noble Metal Nanostructures on 2D Metal-Organic Framework Nanosheets To Catalyze Hydrogen Evolution.

Rational hybridization of two-dimensional (2D) nanomaterials with extrinsic species has shown great promise for a wide range of applications. To date, rational design and engineering of heterostructures based on 2D metal-organic frameworks (MOFs) has been rather limited. Herein, we report an efficient strategy to construct noble metal/2D MOF heterostructures, featuring the utilization of surface oxygen sites from uncoordinated MOF ligands. The incorporation of highly dispersed noble metal nanoparticles (e.g., Pt and Pd) with modulated electronic structure is enabled on a surfactant-free MOF surface. As a proof-of-concept demonstration, the 2D Ni-MOF@Pt hybrid with well-defined interfaces is applied to boost the electrochemical hydrogen evolution reaction (HER) and delivers decent electrocatalytic activity under both acidic and alkaline conditions. The present results are expected to provide new insights into furnishing MOFs with extended functionalities and applications.

Low-Coordinate Iridium Oxide Confined on Graphitic Carbon Nitride for Highly Efficient Oxygen Evolution.

Highly active and durable electrocatalysts for the oxygen evolution reaction (OER) is greatly desired. Iridium oxide/graphitic carbon nitride (IrO2 /GCN) heterostructures are designed with low-coordinate IrO2 nanoparticles (NPs) confined on superhydrophilic highly stable GCN nanosheets for efficient acidic OER. The GCN nanosheets not only ensure the homogeneous distribution and confinement of IrO2 NPs but also endows the heterostructured catalyst system with a superhydrophilic surface, which can maximize the exposure of active sites and promotes mass diffusion. The coordination number of Ir atoms is decreased owing to the strong interaction between IrO2 and GCN, leading to lattice strain and increment of electron density around Ir sites and hence modulating the attachment between the catalyst and reaction intermediates. The optimized IrO2 /GCN heterostructure delivers not only by far the highest mass activity among the reported IrO2 -based catalysts but also decent durability.

Platinum/Nickel Bicarbonate Heterostructures towards Accelerated Hydrogen Evolution under Alkaline Conditions.

Heterostructured nanomaterials, generally have physicochemical properties that differ from those of the individual components, and thus have potential in a wide range of applications. New platinum (Pt)/nickel bicarbonate (Ni(HCO3 )2 ) heterostructures are designed for an efficient alkaline hydrogen evolution reaction (HER). Notably, the specific and mass activity of Pt in Pt/Ni(HCO3 )2 are substantially improved compared to the bare Pt nanoparticles (NPs). The Ni(HCO3 )2 provides abundant water adsorption/dissociation sites and modulate the electronic structure of Pt, which determine the elementary reaction kinetics of alkaline HER. The Ni(HCO3 )2 nanoplates offer a platform for the uniform dispersion of Pt NPs, ensuring the maximum exposure of active sites. The results demonstrate that, Ni(HCO3 )2 is an effective catalyst promoter for alkaline HER.

Alloy-Based Anode Materials toward Advanced Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are considered as promising alternatives to lithium-ion batteries owing to the abundant sodium resources. However, the limited energy density, moderate cycling life, and immature manufacture technology of SIBs are the major challenges hindering their practical application. Recently, numerous efforts are devoted to developing novel electrode materials with high specific capacities and long durability. In comparison with carbonaceous materials (e.g., hard carbon), partial Group IVA and VA elements, such as Sn, Sb, and P, possess high theoretical specific capacities for sodium storage based on the alloying reaction mechanism, demonstrating great potential for high-energy SIBs. In this review, the recent research progress of alloy-type anodes and their compounds for sodium storage is summarized. Specific efforts to enhance the electrochemical performance of the alloy-based anode materials are discussed, and the challenges and perspectives regarding these anode materials are proposed.