Single-atom catalysts based on metal−N 4 moieties and anchored on carbon supports (defined as M−N−C) are promising for oxygen reduction reaction (ORR). Among those, M−N−C catalysts with 4d and 5d transition metal (TM 4d,5d ) centers are much more durable and not susceptible to the undesirable Fenton reaction, especially compared with 3d transition metal based ones. However, the ORR activity of these TM 4d,5d −N− C catalysts is still far from satisfactory; thus far, there are few discussions about how to accurately tune the ligand fields of singleatom TM 4d,5d sites in order to improve their catalytic properties. Herein, we leverage single-atom Ru−N−C as a model system and report an S-anion coordination strategy to modulate the catalyst's structure and ORR performance. The S anions are identified to bond with N atoms in the second coordination shell of Ru centers, which allows us to manipulate the electronic configuration of central Ru sites. The S-anion-coordinated Ru−N−C catalyst delivers not only promising ORR activity but also outstanding longterm durability, superior to those of commercial Pt/C and most of the near-term single-atom catalysts. DFT calculations reveal that the high ORR activity is attributed to the lower adsorption energy of ORR intermediates at Ru sites. Metal−air batteries using this catalyst in the cathode side also exhibit fast kinetics and excellent stability.

Developing low-cost, high performance, stable non-noble bifunctional electrocatalysts for overall water splitting is of great importance for future energy supplement. Despite recent advances in the synthesis of transition metal selenide nanostructures, the fabrication of porous nanosheet based binder-free electrode with more active sites remains a major challenge. Herein, the self-templating construction of a porous CoSe2 nanosheet array on carbon cloth (p-CoSe2/CC) has been reported by vapor selenizing the preprepared α-Co­(OH)2 nanosheet array precursor. Arising from large active surface area, fast diffusion of generated gas and strong structural stability, the as-obtained p-CoSe2/CC can serve as an efficient bifunctional electrocatalyst for both OER and HER in alkaline electrolyte, with a current density of 10 mA cm–2 at overpotential of 243 mV for OER and 138 mV for HER, respectively. Moreover, when p-CoSe2/CC is assembled as an alkaline electrolyzor, it only needs a cell voltage of 1.62 V at 10 mA cm–2 and shows excellent long-term stability of 20 h. The versatile fabrication strategy with self-templated porous structure proves a new way to construct other advanced metal selenide for energy conversion and storage.

The exploration of indurative and stable low-cost catalysts for hydrogen evolution reaction (HER) is of great importance for hydrogen energy economy, but it still faces challenges. Herein, we report a Cl-doped Ni 3 S 2 (Cl−Ni 3 S 2 ) nanoplate catalyst vertically grown on Ni foam with outstanding activity and durability for HER, which only requires an overpotential of 67 mV to reach a current density of 10 mA cm −2 in alkaline media and exhibits negligible degradation after 30 h of operation. Both the advanced X-ray absorption fine structure (XAFS) and density functional theory (DFT) calculation validate that Cl doping can optimize the electronic structure and the intrinsic activity of Ni 3 S 2 . This study devoted to the revelation of the impact of ionic doping on the activity of catalysts at the atomic scale can provide the direction for the rational design of novel and advanced HER electrocatalysts.

Exploiting active and stable non‐precious metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at large current density plays a key role in realizing large‐scale industrial hydrogen generation. Herein, a self‐supported microporous Ni(OH)x/Ni3S2 heterostructure electrocatalyst on nickel foam (Ni(OH)x/Ni3S2/NF) that possesses super‐hydrophilic property through an electrochemical process is rationally designed and fabricated. Benefiting from the super‐hydrophilic property, microporous feature, and self‐supported structure, the electrocatalyst exhibits an exceptional HER performance at large current density in 1.0 M KOH, only requiring low overpotential of 126, 193, and 238 mV to reach a current density of 100, 500, and 1000 mA cm−2, respectively, and displaying a long‐term durability up to 1000 h, which is among the state‐of‐the‐art non‐precious metal electrocatalysts. Combining hard X‐rays absorption spectroscopy and first‐principles calculation, it also reveals that the strong electronic coupling at the interface of the heterostructure facilitates the dissociation of H2O molecular, accelerating the HER kinetics in alkaline electrolyte. This work sheds a light on developing advanced non‐precious metal electrocatalysts for industrial hydrogen production by means of constructing a super‐hydrophilic microporous heterostructure.