The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (∼65 kcal mol), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@CN). The Ru@CN electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H s in 0.5 M HSO solution; 0.75 H s in 1.0 M KOH solution) and small overpotentials at 10 mA cm (13.5 mV in 0.5 M HSO solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

Developing efficient and stable electrocatalysts is crucial for the electrochemical production of pure and clean hydrogen. For practical applications, an economical and facile method of producing catalysts for the hydrogen evolution reaction (HER) is essential. Here, we report ruthenium (Ru) nanoparticles uniformly deposited on multi-walled carbon nanotubes (MWCNTs) as an efficient HER catalyst. The catalyst exhibits the small overpotentials of 13 and 17 mV at a current density of 10 mA cm-2 in 0.5 M aq. H 2 SO 4 and 1.0 M aq. KOH, respectively, surpassing the commercial Pt/C (16 mV and 33 mV). Moreover, the catalyst has excellent stability in both media, showing almost "zeroloss" during cycling. In a real device, the catalyst produces 15.4% more hydrogen per power consumed, and shows a higher Faradaic efficiency (92.28%) than the benchmark Pt/C (85.97%). Density functional theory calculations suggest that Ru-C bonding is the most plausible active site for the HER.

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The hydrogen evolution reaction (HER) is one of the most important pathways for producing pure and clean hydrogen. Although platinum (Pt) is the most efficient HER electrocatalyst, its practical application is significantly hindered by high-cost and scarcity. In this work, an MoC with incorporated Mo vacancies and macroporous inverse opal-like (IOL) structure (MoC-IOL) was synthesized and studied as a low-cost efficient HER electrocatalyst. The macroporous IOL structure was controllably fabricated using a facile-hard template strategy. As a result of the combined benefits of the Mo vacancies and structural advantages, including appropriate hydrogen binding energy, large exposed surface, robust IOL structure and fast mass/charge transport, the synthesized MoC-IOL exhibited significantly enhanced HER electrocatalytic performance with good stability, with performance comparable or superior to Pt wire in both acidic and alkaline solutions.

Electrode materials exploiting multielectron-transfer processes are essential components for large-scale energy storage systems. Organic-based electrode materials undergoing distinct molecular redox transformations can intrinsically circumvent the structural instability issue of conventional inorganic-based host materials associated with lattice volume expansion and pulverization. Yet, the fundamental mechanistic understanding of metal-organic coordination polymers toward the reversible electrochemical processes is still lacking. Herein, we demonstrate that metal-dependent spatial proximity and binding affinity play a critical role in the reversible redox processes, as verified by combined C solid-state NMR, X-ray absorption spectroscopy, and transmission electron microscopy. During the electrochemical lithiation, in situ generated metallic nanoparticles dispersed in the organic matrix generate electrically conductive paths, synergistically aiding subsequent multielectron transfer to π-conjugated ligands. Comprehensive screening on 3d-metal-organic coordination polymers leads to a high-capacity electrode material, cobalt-2,5-thiophenedicarboxylate, which delivers a stable specific capacity of ∼1100 mA h g after 100 cycles.