Competitive Coordination‐Pairing between Ru Clusters and Single‐Atoms for Efficient Hydrogen Evolution Reaction in Alkaline Seawater

Abstract

The coordination environment of Ru centers determines their catalytic performance, however, much less attention is focused on cluster‐induced charge transfer in a Ru single‐atom system. Herein, by density functional theory (DFT) calculations, a competitive coordination‐pairing between Ru clusters (RuRu bond) and single‐atoms (RuO bond) is revealed leading to the charge redistribution between Ru and O atoms in ZnFe2O4 units which share more free electrons to participate in the hydrogen desorption process, optimizing the proton adsorption and hydrogen desorption. Thus, a clicking confinement strategy for building a competitive coordination‐pairing between Ru clusters and single‐atoms anchored on ZnFe2Ox nanosheets over carbon via RuO ligand (Ru1,n‐ZnFe2Ox‐C) is proposed. Benefiting from the optimized coordination effect and the electronic synergy between Ru clusters and single‐atoms, such a catalyst demonstrates the excellent activity and excellent stability in alkaline and seawater media, which has exceptional hydrogen evolution reaction activity with overpotentials as low as 10.1 and 15.9 mV to reach the current density of 10 mA cm−2 in alkaline and seawater media, respectively, higher than that of commercial Pt/C catalysts as a benchmark. Furthermore, it owns remarkably outstanding mass activity, approximately 2 and 8 times higher than that of Pt catalysts in alkaline and seawater media, respectively.

Hierarchical porous NiFe-P@NC as an efficient electrocatalyst for alkaline hydrogen production and seawater electrolysis at high current density

“…23,24 Cl − deposition on the cathode surface leads to poor electrode stability and the inferior efficiency of the catalyst. [25][26][27][28] Therefore, the exploration of efficient and highly stable electrocatalysts are crucial to accelerate the development of seawater splitting. [29][30][31] Tremendous efforts have been devoted to exploring efficient nonprecious catalysts.…”

Synergistic Acid Hydrogen Evolution of Neighboring Pt Single Atoms and Clusters: Understanding Their Superior Activity and Mechanism

“…Actually, we have found that Pt single atoms and clusters have a synergistic effect on alkaline HER . Besides, the synergistic catalytic effect of single atoms and clusters or nanoparticles also appears in many other reactions. − Therefore, it is of great significance to construct a multi-site catalyst model and reveal the synergistic catalytic mechanism between active sites for the development of high-performance Pt-based acidic HER catalysts and maximizing platinum utilization.…”

Electrode Materials of Cobaltous Fluoride for Supercapacitor and Electrocatalysis Applications

“…Water splitting to produce hydrogen is a green and environmentally friendly strategy. However, the sluggish kinetic properties of hydrogen evolution reaction (HER) require an efficient catalyst to bridge the gap between the theoretical potential and the actual required potential, that is, to obtain a great current density at a little overpotential [20–21] . The better electrocatalytic performance is achieved by precious metal catalysts such as metallic platinum, but their lack of natural reserves, expensive and unstable, thus greatly limiting their further application in real‐life applications [22–24] .…”

“…However, the sluggish kinetic properties of hydrogen evolution reaction (HER) require an efficient catalyst to bridge the gap between the theoretical potential and the actual required potential, that is, to obtain a great current density at a little overpotential. [20][21] The better electrocatalytic performance is achieved by precious metal catalysts such as metallic platinum, but their lack of natural reserves, expensive and unstable, thus greatly limiting their further application in real-life applications. [22][23][24] Consequently, the development of nonprecious metal-based catalysts that are abundant in nature, low cost, efficient, and with long-term stability is an effective strategy to commercialize clean and green energy.…”