With the development of renewable energy systems, clean hydrogen is burgeoning as an optimal alternative to fossil fuels, in which its application is promising to retarding the global energy and environmental crisis. The hydrogen evolution reaction (HER), capable of producing high-purity hydrogen rapidly in electrocatalytic water splitting, has received much attention. Abundant research about HER has been done, focusing on advanced electrocatalyst design with high efficiency and robust stability. As potential HER catalysts, metal nanoclusters (MNCs) have been studied extensively. They are composed of several to a hundred metal atoms, with sizes being comparable to the Fermi wavelength of electrons, that is, < 2.0 nm. Different from metal atoms/nanoparticles, they exhibit unique catalytic properties due to their quantum size effect and low-coordination environment. In this review, the activity-enhancing approaches of MNCs applied in HER electrocatalysis are mainly summarized. Furthermore, recent progress in MNCs classified with different stabilization strategies, that is, the freestanding MNCs, MNCs with organic, metal and carbon supports, are introduced. Finally, the current challenges and deficiencies of these MNCs for HER are prospected.

Advances in the Electrocatalytic Hydrogen Evolution Reaction by Metal Nanoclusters-based Materials.

The sluggish kinetics of oxygen evolution reaction (OER) hampers the conversion of renewable energies into hydrogen through an electrocatalytic process. Then, the hydrazine oxidation reaction (HzOR) is a promising anodic reaction to substitute OER, which can decrease the water-splitting voltage. Herein, self-supported ruthenium-doped cuprous oxide nanochains were synthesized on commercial copper foam (Ru-Cu2O/CF). The Ru-Cu2O/CF provides superior hydrogen evolution reaction (HER) and HzOR performances owing to its specific morphology, superhydrophilic surface, porous support and Ru doping. When used in alkaline or neutral electrolytes, the Ru-Cu2O/CF is capable of driving 10 mA cm−2 only at 31 and 51 mV, respectively. In HzOR, it is possible to achieve a superlow potential of − 41 mV at 10 mA cm−2. In an electrolytic cell with a Ru-Cu2O/CF both as cathode and anode, a voltage of 17.4 mV is needed to reach 10 mA cm−2, which is powered by renewable energies. 

Ruthenium-doped 3D Cu2O Nanochains as Efficient Electrocatalyst towards Hydrogen Evolution and Hydrazine Oxidation

B-doped MoS2 for nitrate electroreduction to ammonia.

Rechargeable aqueous Zn–CO2 batteries show great promise in meeting severe environmental problems and energy crises due to their combination of CO2 utilization and energy output, as well as advantages of high theoretical energy density, abundant raw materials, and high safety. Developing high‐efficiency and stable CO2 reduction reaction (CO2RR) electrocatalysts is of critical importance for the promotion of this technology. Atomically dispersed metal‐based catalysts (ADMCs), with extremely high atom‐utilization efficiency, tunable coordination environments, and superior intrinsic catalytic activity, are emerging as promising candidates for Zn–CO2 batteries. Herein, some recent developments in atomically dispersed metal‐based catalysts for Zn–CO2 batteries are summarized, including transition metal and non‐transition metal sites. Moreover, various synthetic strategies, characterization methods, and the relationship between active site structures and CO2RR activity/Zn–CO2 battery performance are introduced. Finally, some challenges and perspectives are also proposed for the future development of ADMCs in Zn–CO2 batteries.

Atomically Dispersed Metal‐Based Catalysts for Zn–CO2 Batteries

A dual-functional Bi-doped Co3O4 nanosheet array towards high efficiency 5-hydroxymethylfurfural oxidation and hydrogen production.

Cu2O-Derived PtCu Nanoalloy toward Energy-Efficient Hydrogen Production via Hydrazine Electrolysis under Large Current Density

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Cu2O-Derived PtCu Nanoalloy toward Energy-Efficient Hydrogen Production via Hydrazine Electrolysis under Large Current Density