Synergistic Electrocatalysts for Alkaline Hydrogen Oxidation and Evolution Reactions

Rational design and preparation of single‐atom catalysts provide a promising strategy to significantly improve the electrocatalytic activity for water splitting. In particular, single atoms anchored at cationic vacancies can enhance the stability of the catalysts and improve reaction kinetics. In this work, Pt single atoms are loaded at layered α‐Ni2/3Fe1/3(OH)2 by oxidizing Fe2+ with H2PtCl6, and specifically, Pt atoms are anchored at in situ generated iron cationic vacancies during the process, resulting in stabilized Pt single atoms in the surface of α‐Ni2/3Fe1/3(OH)2 with the maximum loading of ≈6.15 wt%. The Pt single atoms not only act as active sites for hydrogen evolution reaction but also regulate the electronic structure of NiFe hydroxides and activate Ni atoms adjacent to Pt for oxygen evolution reaction. Therefore, the water‐splitting electrolyzer assembled with such a bifunctional catalyst shows a smaller overpotential than that with RuO2 and 20 wt% Pt/C catalysts as the anode and cathode, respectively, and efficient solar‐to‐hydrogen conversion. The results demonstrate the practical application of single‐atom Pt catalysts with low cost, large loading, and facile preparation route.

In Situ Anchoring Massive Isolated Pt Atoms at Cationic Vacancies of α‐NixFe1‐x(OH)2 to Regulate the Electronic Structure for Overall Water Splitting

Oxygen reduction reaction on Pt-based electrocatalysts: Four-electron vs. two-electron pathway

Catalysts featuring dinuclear metal sites are regarded as superior systems compared with their counterparts with mononuclear metal sites. The dinuclear metal sites in catalysts with appropriate spatial separations and geometric configurations can confer the dinuclear metal synergistic catalysis (DMSC) effect, and thus boost the catalytic performance, in particular for reactions involving multiple reactants, intermediates and products. In this review, we summarize the related reports on the design and synthesis of both homogeneous and heterogeneous dinuclear metal catalysts, and their applications in energy conversion reactions, including photo-/electro-catalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), CO2 reduction reaction (CO2RR), and N2 reduction reaction (N2RR). Particularly, we focus on the analysis of the relationship between the catalyst structure and catalytic performances, where the design principles are presented. Finally, we discuss the challenges in the design and preparation of dinuclear metal catalysts with the DMSC effect and present a perspective on the future development of dinuclear metal catalysts in energy conversion. This review aims to comprehensively summarize the up-to-date research progress on the synthesis and energy-related application of dinuclear metal catalysts and provide guidance for designing energy-conversion catalysts with superior performances.

Dinuclear metal synergistic catalysis for energy conversion.

Hydrazine-assisted water electrolysis presents a promising energy conversion technology for highly efficient hydrogen production. Owing to the potential coincidence region between hydrogen evolution reaction (HER) and hydrazine electro-oxidation, hydrazine oxidation reaction (HzOR) exhibits specific advantages on strategy combination, device construction, and application expansion. Herein, we report a bifunctional electrocatalyst of porous Ni foam-supported interfacial heterogeneous Ni2P/Co2P microspheres (denoted NiCoP/NF), which takes full advantage of this potential coincidence region. Thanks to the 3D microsphere structure and strong interfacial coupling effects between Ni2P and Co2P, NiCoP/NF demonstrates excellent bifunctional electrocatalytic performance, requiring ultralow overpotentials of 70 and 230 mV at 10 mA cm-2 for HER and HzOR, respectively. When using NiCoP/NF as both electrodes, HzOR-assisted water electrolysis exhibits considerably decreased potentials compared with the electro-oxidation of other chemical substrates. Furthermore, the potential coincidence region of 0.1 V makes the application of self-activated/propelled hydrazine-assisted alkaline seawater electrolysis, hydrazine-containing wastewater treatment, and Zn-hydrazine (Zn-Hz) battery realistic. The concept of potential coincidence region provided in this work has significant implications for water electrolysis and other related applications.

Taking Advantage of Potential Coincidence Region: Advanced Self-Activated/Propelled Hydrazine-Assisted Alkaline Seawater Electrolysis and Zn-Hydrazine Battery.

CoMo2S4 with Superior Conductivity for Electrocatalytic Hydrogen Evolution: Elucidating the Key Role of Co

Di-nuclear metal synergistic catalysis: Ni2Mo6S6O2/MoS2 two-dimensional nanosheets for hydrogen evolution reaction

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CoMo2S4 with Superior Conductivity for Electrocatalytic Hydrogen Evolution: Elucidating the Key Role of Co

Di-nuclear metal synergistic catalysis: Ni2Mo6S6O2/MoS2 two-dimensional nanosheets for hydrogen evolution reaction