Minireview: Ni–Fe and Ni–Co Metal–Organic Frameworks for Electrocatalytic Water‐Splitting Reactions

Electrolysis is one of the clean, environmentally friendly, and sustainable pathways to produce hydrogen for renewable energy storage. However, to make electrolysis a competitive technology for hydrogen production, developing nonprecious metal‐based catalysts for oxygen evolution reaction (OER) is mandatory. Several new classes of electrocatalysts are developed with outstanding OER catalytic activity, stability, and commercial viability. Owing to the structural diversity, porosity, and accessibility of catalytically active metal centers, nickel‐based metal–organic frameworks (MOFs) are intensively explored as OER catalysts. In particular, bi‐ and trimetallic Ni MOFs with Fe and Co as additional metal nodes show excellent OER activity which can be tailored through the fine tuning of the metal compositions. Herein, the current state of research in Ni‐based MOFs as OER catalyst materials for alkaline electrolysis is presented. Strategies to improve the catalytic performance like compositional variations, choice of synthetic routes, and support materials are presented. Furthermore, OER activities are compared and presented based on the performance metrics (current density, overpotential, and Tafel slopes). Finally, concluding remarks featuring the key findings in Ni‐based MOFs and the possible rooms for future developments are summarized

Use of suspended particles as a new approach to increase the active electrode area in water electrolysis experiments

The development of base metal electrodes that can act as active and stable oxygen generating electrodes in water electrolysis systems, especially at low pH levels, remains a challenge. The use of suspensions as electrolytes for water splitting has until recently been limited to photoelectrocatalytic approaches. A high current density (j=30 mA/cm2) for water electrolysis has been achieved at a very low oxygen evolution reaction (OER) potential (E=1.36 V vs. RHE) using a SnO2/H2SO4 suspension-based electrolyte in combination with a steel anode. More importantly, the high charge-to-oxygen conversion rate (Faraday efficiency of 88% for OER at j=10 mA/cm2 current density). Since cyclic voltammetry (CV) experiments show that oxygen evolution starts at a low, but not exceptionally low, potential, the reason for the low potential in chronoamperometry (CP) tests is an increase in the active electrode area, which has been confirmed by various experiments. For the first time, the addition of a relatively small amount of solids to a clear electrolyte has been shown to significantly reduce the overpotential of the OER in water electrolysis down to the 100 mV region, resulting in a remarkable reduction in anode wear while maintaining a high current density

Increased Readiness for Water Splitting: NiO-Induced Weakening of Bonds in Water Molecules as Possible Cause of Ultra-Low Oxygen Evolution Potential

Bookholt T, Qin X, Lilli B, et al. Increased Readiness for Water Splitting: NiO-Induced Weakening of Bonds in Water Molecules as Possible Cause of Ultra-Low Oxygen Evolution Potential. Small . 2024: 2310665.The development of non-precious metal-based electrodes that actively and stably support the oxygen evolution reaction (OER) in water electrolysis systems remains a challenge, especially at low pH levels. The recently published study has conclusively shown that the addition of haematite to H2 SO4 is a highly effective method of significantly reducing oxygen evolution overpotential and extending anode life. The far superior result is achieved by concentrating oxygen evolution centres on the oxide particles rather than on the electrode. However, unsatisfactory Faradaic efficiencies of the OER and hydrogen evolution reaction (HER) parts as well as the required high haematite load impede applicability and upscaling of this process. Here it is shown that the same performance is achieved with three times less metal oxide powder if NiO/H2 SO4 suspensions are used along with stainless steel anodes. The reason for the enormous improvement in OER performance by adding NiO to the electrolyte is the weakening of the intramolecular O─H bond in the water molecules, which is under the direct influence of the nickel oxide suspended in the electrolyte. The manipulation of bonds in water molecules to increase the tendency of the water to split is a ground-breaking development, as shown in this first example. © 2024 The Authors. Small published by Wiley-VCH GmbH