Electrochemical water splitting is a common way to produce hydrogen gas, but the sluggish kinetics of the oxygen evolution reaction (OER) significantly limits the overall energy conversion efficiency of water splitting. In this work, a highly active and stable, meso–macro hierarchical porous Ni₃S₄ architecture, enriched in Ni³⁺ is designed as an advanced electrocatalyst for OER. The obtained Ni₃S₄ architectures exhibit a relatively low overpotential of 257 mV at 10 mA cm⁻² and 300 mV at 50 mA cm⁻². Additionally, this Ni₃S₄ catalyst has excellent long‐term stability (no degradation after 300 h at 50 mA cm⁻²). The outstanding OER performance is due to the high concentration of Ni³⁺ and the meso–macro hierarchical porous structure. The presence of Ni³⁺ enhances the chemisorption of OH⁻, which facilitates electron transfer to the surface during OER. The hierarchical porosity increases the number of exposed active sites, and facilitates mass transport. A water‐splitting electrolyzer using the prepared Ni₃S₄ as the anode catalyst and Pt/C as the cathode catalyst achieves a low cell voltage of 1.51 V at 10 mA cm⁻². Therefore, this work provides a new strategy for the rational design of highly active OER electrocatalysts with high valence Ni³⁺ and hierarchical porous architectures.

This review presents the recent developments of electrodeposited MOF films and their corresponding applications in different areas.

Innovative bimetallic MOFs offer more possibilities to further tailor the properties of MOFs, which have attracted great attention for wide applications. However, it is still a great challenge to rationally design bimetallic MOFs due to the lack of a tunable and reasonable hybrid structure architecture. Herein, a new series of bimetallic metal–organic frameworks (MOFs) with tunable pillar linkers were prepared by a one-step synthesis method. These bimetallic MOFs retain the same crystal structure when the mole fraction (based on metal) of the two metals changes from 0 to 1 and both metal ions occupy random nodal positions. The incorporation of a second metal cation has a large influence on the intrinsic properties (e.g. thermal stabilities and band gaps) of the MOFs. Furthermore, these bimetallic MOFs were used as self-sacrificial templates to prepare bimetal oxide catalysts for the oxygen evolution reaction (OER). After pyrolysis, a porous and hierarchical honeycomb-like structure with carbon network covered (bi)metal oxides is formed. Among all the bimetallic MOF-derived catalysts, CoNi1@C showed the best performance for the OER with the lowest Tafel slopes (55.6 mV dec⁻¹) and overpotentials (335 mV on a glassy carbon electrode and 276 mV on Ni foam) at a current density of 10 mA cm⁻², which is higher than those of state-of-the-art Co–Ni mixed oxide catalysts derived from MOFs for the OER. Our results indicate that the incorporation of a second metal ion is a promising strategy to tailor the properties of MOFs. More importantly, this new bimetallic MOF family with tunable linkers is expected to serve as a flexible assembly platform to offer broad possibilities for practical applications of MOFs.

Different surfactants were used in a typical hydrothermal process for controlling the morphology of the Co₃O₄ nanowire superstructure on Ni foam. It is easy for the Co₃O₄ nanowires to self-organize into nanowire microspheres on Ni foam in the absence of surfactants. And the nanowire microspheres gradually unfold into nanowire paddy fields with the addition of nonionic, cationic and anionic surfactants, respectively. The results of BET and electrochemical measurements show that the specific surface area and capacitance first decrease and then increase with the change in the Co₃O₄ superstructure morphology. Among these electrodes, the Co₃O₄ electrode with paddy like nanowires shows an outstanding specific capacitance of 1217.4 F g⁻¹ and areal specific capacitance as high as 6087 mF cm⁻² at 0.7 A g⁻¹ with high mass loading (5 mg cm⁻²), good power capability (showing a high specific capacitance of 835.1 F g⁻¹ (4176 mF cm⁻²) at 5 A g⁻¹), excellent cycling stability and high columbic efficiency (∼100%). This exceptional performance is benefited from the almost monodispersed nanowire morphology and high specific surface area (121.4 m² g⁻¹). At the same time, the asymmetric supercapacitor, employing the Co₃O₄ electrode with paddy-like nanowires as the positive electrode and the activated carbon electrode as the negative electrode, was successfully assembled. It shows a high specific energy and good long-term electrochemical stability. All these impressive results demonstrate that the Co₃O₄ electrode with paddy-like nanowires is promising for practical applications in supercapacitors.

Despite the significant advances in preparing carbon-metal oxide composite electrodes, strategies for seamless interconnecting of these two materials without using binders are still scarce. Herein we design a novel method for in situ synthesis of porous 2D-layered carbon–metal oxide composite electrode. Firstly, 2D-layered Ni-Co mixed metal-organic frameworks (MOFs) are deposited directly on nickel foam by anodic electrodeposition. Subsequent pyrolysis and activation procedure lead to the formation of carbon–metal oxides composite electrodes. Even with an ultrahigh mass loading of 13.4 mg cm−2, the as-prepared electrodes exhibit a superior rate performance of 93% (from 1 to 20 mA cm−2), high capacitance (2098 mF cm−2 at a current density of 1 mA cm−2), low resistance and excellent cycling stability, making them promising candidates for practical supercapacitor application. As a proof of concept, several MOF derived electrodes with different metal sources have also been prepared successfully via the same route, demonstrating the versatility of the proposed method for the preparation of binder-free carbon–metal oxide composite electrodes for electrochemical devices.status: publishe

The electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are fundamental processes in a range of energy conversion devices such as fuel cells and metal–air batteries. ORR and OER both have significant activation barriers, which severely limit the overall performance of energy conversion devices that utilize ORR/OER. Meanwhile, ORR is another very important electrochemical reaction involving oxygen that has been widely investigated. ORR occurs in aqueous solutions via two pathways: the direct 4-electron reduction or 2-electron reduction pathways from O₂ to water (H₂O) or from O₂ to hydrogen peroxide (H₂O₂). Noble metal electrocatalysts are often used to catalyze OER and ORR, despite the fact that noble metal electrocatalysts have certain intrinsic limitations, such as low storage. Thus, it is urgent to develop more active and stable low-cost electrocatalysts, especially for severe environments (e.g., acidic media). Theoretically, an ideal oxygen electrocatalyst should provide adequate binding to oxygen species. Transition metals not belonging to the platinum group metal-based oxides are a low-cost substance that could give a d orbital for oxygen species binding. As a result, transition metal oxides are regarded as a substitute for typical precious metal oxygen electrocatalysts. However, the development of oxide catalysts for oxygen reduction and oxygen evolution reactions still faces significant challenges, e.g., catalytic activity, stability, cost, and reaction mechanism. We discuss the fundamental principles underlying the design of oxide catalysts, including the influence of crystal structure, and electronic structure on their performance. We also discuss the challenges associated with developing oxide catalysts and the potential strategies to overcome these challenges.