Exploring noble-metal-free electrocatalysts with high efficiency for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) holds promise for advancing the production of H2 fuel through water splitting. Herein, one-pot synthesis was introduced for MoS2–Ni3S2 heteronanorods supported by Ni foam (MoS2–Ni3S2 HNRs/NF), in which the Ni3S2 nanorods were hierarchically integrated with MoS2 nanosheets. The hierarchical MoS2–Ni3S2 heteronanorods allow not only the good exposure of highly active heterointerfaces but also the facilitated charge transport along Ni3S2 nanorods anchored on conducting nickel foam, accomplishing the promoted kinetics and activity for HER, OER, and overall water splitting. The optimal MoS2–Ni3S2 HNRs/NF presents low overpotentials (η10) of 98 and 249 mV to reach a current density of 10 mA cm–2 in 1.0 M KOH for HER and OER, respectively. Assembled as an electrolyzer for overall water splitting, such heteronanorods show a quite low cell voltage of 1.50 V at 10 mA cm–2 and remarkable stability for more than 48 h, which are among the best values of current noble-metal-free electrocatalysts. This work elucidates a rational design of heterostructures as efficient electrocatalysts, shedding some light on the development of functional materials in energy chemistry.

MoC–Mo2C heteronanowires accomplished via controlled carbonization are efficient in the hydrogen evolution reaction due to a synergistic enhancement.

Efficient hydrogen evolution reaction (HER) over noble‐metal‐free electrocatalysts provides one of the most promising pathways to face the energy crisis. Herein, facile cobalt‐doping based on Co‐modified MoOx–amine precursors is developed to optimize the electrochemical HER over Mo2C nanowires. The effective Co‐doping into Mo2C crystal structure increases the electron density around Fermi level, resulting in the reduced strength of Mo–H for facilitated HER kinetics. As expected, the Co‐Mo2C nanowires with an optimal Co/Mo ratio of 0.020 display a low overpotential (η10 = 140 and 118 mV for reaching a current density of –10 mA cm−2; η100 = 200 and 195 mV for reaching a current density of –100 mA cm−2), a small Tafel slope (39 and 44 mV dec−1), and a low onset overpotential (40 and 25 mV) in 0.5 m H2SO4 and 1.0 m KOH, respectively. This work highlights a feasible strategy to explore efficient electrocatalysts via engineering on composition and nanostructure.

Electronic regulation of Mo2C and thus intrinsically improved HER activity via balanced Volmer and Heyrovsky/Tafel steps.

A porous nanoMoC@GS electrocatalyst consists of ultrafine MoC nanoparticles encapsulated by ultrathin graphite shells and exhibits a remarkable HER activity.