Electrocatalysts with single metal atoms as active sites have received increasing attention owing to their high atomic utilization efficiency and exotic catalytic activity and selectivity. This review aims to provide a comprehensive summary on the recent development of such single-atom electrocatalysts (SAECs) for various energy-conversion reactions. The discussion starts with an introduction of the different types of SAECs, followed by an overview of the synthetic methodologies to control the atomic dispersion of metal sites and atomically resolved characterization using state-of-the-art microscopic and spectroscopic techniques. In recognition of the extensive applications of SAECs, the electrocatalytic studies are dissected in terms of various important electrochemical reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), and nitrogen reduction reaction (NRR). Examples of SAECs are deliberated in each case in terms of their catalytic performance, structure−property relationships, and catalytic enhancement mechanisms. A perspective is provided at the end of each section about remaining challenges and opportunities for the development of SAECs for the targeted reaction.

kinetics of ORR is around five orders of magnitude slower than that of HOR, thereby requiring a much higher Pt loading in the cathode along with more active and durable ORR electrocatalysts than pure Pt catalysts. [1] This requirement presents challenges for the development of advanced cathode catalysts with lower cost, higher activity and higher durability than Pt. Meanwhile, traditional alkaline fuel cells (AFCs) working on concentrated 30−45% KOH electrolytes gained little attention for decades mainly due to their high sensitivity to atmospheric CO 2 . [2,3] The OH − ions in the electrolyte react with CO 2 and form K 2 CO 3 , which can precipitate out as solid crystals, blocking pores in the electrode and gas diffusion layer. In addition, the consumption of OH − reduces the conductivity of the electrolyte. This issue is addressed by replacing KOH solution with a solid anion exchange membrane (AEM) without mobile cations. An AMFC offers several important advantages over PEMFCs, including: 1) low dissolution rates of catalysts, allowing the use of less expensive Pt-free electrocatalysts; 2) wide selections of materials and components that are stable at high pH; and 3) inexpensive solid electrolytes that do not need fluorinated ionomers. Despite their promise, AMFCs are still in the early development stage and have not been systematically investigated due to the lack of highly conductive and durable AEMs. The recent development of highly conductive The rapid progress of proton exchange membrane fuel cells (PEMFCs) and alkaline exchange membrane fuel cells (AMFCs) has boosted the hydrogen economy concept via diverse energy applications in the past decades. For a holistic understanding of the development status of PEMFCs and AMFCs, recent advancements in electrocatalyst design and catalyst layer optimization, along with cell performance in terms of activity and durability in PEMFCs and AMFCs, are summarized here. The activity, stability, and fuel cell performance of different types of electrocatalysts for both oxygen reduction reaction and hydrogen oxidation reaction are discussed and compared. Research directions on the further development of active, stable, and low-cost electrocatalysts to meet the ultimate commercialization of PEMFCs and AMFCs are also discussed.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202006292.

Recent years have witnessed increasing interest in the solution-phase synthesis of atomically precise thiolate-protected gold clusters (Aux ); nonetheless, research on the photocatalytic properties of Aux -semiconductor nanocomposites is still in its infancy. In this work, recently developed glutathione-capped gold clusters and highly ordered nanoporous layer-covered TiO2 nanotube arrays (NP-TNTAs) are employed as nanobuilding blocks for the construction of a well-defined Aux /NP-TNTA heterostructure via a facile electrostatic self-assembly strategy. Versatile photocatalytic performances of the Aux /NP-TNTA heterostructure which acts as a model catalyst, including photocatalytic oxidation of organic pollutant, photocatalytic reduction of aromatic nitro compounds and photoelectrochemical (PEC) water splitting under simulated solar light irradiation, are systematically exploited. It is found that synergistic interaction stemming from monodisperse coverage of Aux clusters on NP-TNTAs in combination with hierarchical nanostructure of NP-TNTAs reinforce light absorption of Aux /NP-TNTA heterostructure especially within visible region, hence contributing to the significantly enhanced photocatalytic and PEC water splitting performances. Moreover, photocatalytic and PEC mechanisms over Aux /NP-TNTA heterostructure are elucidated and corresponding reaction models were presented. It is anticipated that this work could boost new insight for photocatalytic properties of metal-cluster-sensitized semiconductor nanocomposites.