Oxygen evolution reaction (OER) in acidic media usually requires a catalyst with high content of noble Ir or Ru, becoming a bottleneck for the electrochemical water splitting. To address this issue, here we report the fabrication of a RuO2/(Co,Mn)3O4 nanocomposite with low Ru loading (2.51 wt%) as a highly efficient OER catalyst in acidic media (0.5 M H2SO4). Spectroscopic and theoretical studies demonstrate that the introduction of Mn in Co3O4 results in redistribution of electrons and the generation of electron-rich Ru species of the RuO2/(Co,Mn)3O4 catalyst. With modulated electronic properties, the adsorption of O on RuO2/(Co,Mn)3O4 is weakened and the rate determining step, formation of OOH*, of the OER process is therefore accelerated. At such a low Ru loading, RuO2/(Co,Mn)3O4 exhibits superior acidic OER activity (η =270 mV at 10 mA/cm2) and long‐term stability to the benchmark RuO2 catalyst. This work provides a new strategy for the design of cost-effective acidic OER electrocatalysts for energy conversion applications.

Low Ru loading RuO2/(Co,Mn)3O4 nanocomposite with modulated electronic structure for efficient oxygen evolution reaction in acid

Stability and deactivation of OER electrocatalysts: A review

Renewable energy-powered water electrolysis and photocatalytic water splitting are two promising approaches to green hydrogen production. Electrocatalysts and photocatalysts are essential components determining the performance of water electrolyzers and photocatalytic reactors, respectively. Currently, there is a pressing need to develop efficient and stable electrocatalysts and photocatalysts for large-scale deployment of these devices to reach carbon neutrality. Herein, we report the synthesis of single-atom Ir and Ru anchored on mesoporous graphitic carbon nitride (Ir-g-CN and Ru-g-CN), which can be used as electrocatalysts and photocatalysts for the hydrogen evolution reaction (HER). Remarkably, Ru-g-CN shows a high turnover frequency (TOF) of 12.9 and 5.1 s−1 at an overpotential (η) of 100 mV in 0.5 M H2SO4 and 1.0 M KOH, respectively, outperforming Ir-g-CN, commercial Pt/C benchmark and many other advanced HER catalysts reported recently. Moreover, Ru-g-CN can deliver an exceptionally high mass activity of 24.55 and 8.78 A mg−1 at η = 100 mV in acidic and alkaline solutions, meanwhile exhibiting a high apparent current density, which is favorable for practical applications. Additionally, both Ru-g-CN and Ir-g-CN show outstanding catalytic stability, continuously catalyzing the HER in acidic and alkaline conditions for 120 h with minimal degradation. Besides, when used for photocatalytic water splitting, Ru-g-CN can achieve a high hydrogen production rate of 489.7 mmol H2 gRu−1 h−1, and shows good photocatalytic stability. Our density functional theory (DFT) calculations demonstrate that loading Ir and Ru single-atoms on g-CN alters the electronic structure, resulting in a reduced bandgap and improved electrical conductivity, facilitating electron transfer during the catalysis. Moreover, the Gibbs free energy of hydrogen adsorption on Ru-g-CN and Ir-g-CN is also substantially lowered, enhancing HER performance. 

Single-atom Ir and Ru anchored on graphitic carbon nitride for efficient and stable electrocatalytic/photocatalytic hydrogen evolution

Oxygen evolution reaction (OER) is an energy‐determined half‐reaction for water splitting and many other energy conversion processes, such as rechargeable metal–air batteries and CO2 reduction, due to its four‐electron sluggish process. To reduce the energy consumption and cost of these advanced technologies, various transition metal‐based nanomaterials, like metal oxides/hydroxides, nitride, and phosphide are synthesized. Among these, metal–organic framework (MOF)‐based materials are considered as the ideal candidate for the fabrication of efficient OER electrocatalysts owing to their unique physicochemical properties. In this review, the fundamental catalytic mechanisms and key evaluation parameters of OER in acidic and alkaline media are presented first. Then, design strategies for MOF‐based OER catalysts and research progress in the study of the structure–performance relationship are summarized. Subsequently, the recent research advances of MOF‐based OER electrocatalysts in alkaline, acidic, and neutral electrolytes are overviewed. Finally, current challenges and future opportunities are provided under the frame of materials design, theoretical understanding, advanced characterization techniques, and industrial applications.

Metal–Organic Framework‐Based Nanomaterials for Electrocatalytic Oxygen Evolution

Nucleation and growth are critical steps in crystallization, which plays an important role in determining crystal structure, size, morphology, and purity. Therefore, understanding the mechanisms of nucleation and growth is crucial to realize the controllable fabrication of crystalline products with desired and reproducible properties. Based on classical models, the initial crystal nucleus is formed by the spontaneous aggregation of ions, atoms, or molecules, and crystal growth is dependent on the monomer's diffusion and the surface reaction. Recently, numerous in situ investigations on crystallization dynamics have uncovered the existence of nonclassical mechanisms. This review provides a summary and highlights the in situ studies of crystal nucleation and growth, with a particular emphasis on the state-of-the-art research progress since the year 2016, and includes technological advances, atomic-scale observations, substrate- and temperature-dependent nucleation and growth, and the progress achieved in the various materials: metals, alloys, metallic compounds, colloids, and proteins. Finally, the forthcoming opportunities and challenges in this fascinating field are discussed.

In Situ Kinetic Observations on Crystal Nucleation and Growth.

Achieving an efficient and stable oxygen evolution reaction (OER) in an acidic or neutral medium is of paramount importance for hydrogen production via proton exchange membrane water electrolysis (...

Atomic-Step Enriched Ruthenium–Iridium Nanocrystals Anchored Homogeneously on MOF-Derived Support for Efficient and Stable Oxygen Evolution in Acidic and Neutral Media

Bin Wei

Papers

Atomic-Step Enriched Ruthenium–Iridium Nanocrystals Anchored Homogeneously on MOF-Derived Support for Efficient and Stable Oxygen Evolution in Acidic and Neutral Media