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.

Catalysts are at the heart of the hydrogen evolution reaction (HER) for the production of pure and clean hydrogen. For practical applications, the scalable synthesis of efficient HER catalysts, which work in both acidic and alkaline media, is highly desired. In this work, the mechanochemically assisted synthesis of a Ru catalyst with HER performance surpassing Pt in both acidic and alkaline media is reported. Mass production of this Ru catalyst can be achieved via a two-step procedure: the mechanochemical reaction between graphite and dry ice produces edge-carboxylic-acid-functionalized graphene nanoplatelets (CGnP); mixing a Ru precursor and the CGnP in an aqueous medium introduces Ru ions, which coordinate on the CGnP. Subsequent annealing results in uniform Ru nanoparticles (≈2 nm) anchored on the GnP matrix (Ru@GnP). The efficient Ru@GnP catalyst can be easily powered by a single silicon solar cell using a wireless integration device. The self-powered device exhibits robust hydrogen evolution under the irradiation of standard AM 1.5 solar light. This work provides a new opportunity for the low-cost mass production of efficient and stable catalysts for practical applications.

Hydrogen adsorption/desorption behavior plays a key role in hydrogen evolution reaction (HER) catalysis. The HER reaction rate is a trade-off between hydrogen adsorption and desorption on the catalyst surface. Herein, we report the rational balancing of hydrogen adsorption/desorption by orbital modulation using introduced environmental electronegative carbon/nitrogen (C/N) atoms. Theoretical calculations reveal that the empty d orbitals of iridium (Ir) sites can be reduced by interactions between the environmental electronegative C/N and Ir atoms. This balances the hydrogen adsorption/desorption around the Ir sites, accelerating the related HER process. Remarkably, by anchoring a small amount of Ir nanoparticles (7.16 wt%) in nitrogenated carbon matrixes, the resulting catalyst exhibits significantly enhanced HER performance. This includs the smallest reported overpotential at 10 mA cm −2 (4.5 mV), the highest mass activity at 10 mV (1.12 A mg Ir −1 ) and turnover frequency at 25 mV (4.21 H 2 s −1 ) by far, outperforming Ir nanoparticles and commercial Pt/C.

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.

Developing efficient and durable electrocatalysts is key to optimizing the electrocatalytic hydrogen evolution reaction (HER), currently one of the cleanest and most sustainable routes for producing hydrogen. Here, a unique and efficient approach to fabricate and embed uniformly dispersed Ir nanoparticles in a 3D cage‐like organic network (CON) structure is reported. These uniformly trapped Ir nanoparticles within the 3D CON (Ir@CON) effectively catalyze the HER process. The Ir@CON electrocatalyst exhibits high turnover frequencies of 0.66 and 0.20 H2 s−1 at 25 mV and small overpotentials of 13.6 and 13.5 mV while generating a current density of 10 mA cm−2 in 0.5 m H2SO4 and 1.0 m KOH aqueous solutions, respectively, as compared to commercial Pt/C (18 and 23 mV) and Ir/C (20.7 and 28.3 mV). More importantly, the catalyst shows superior stability in both acidic and alkaline media. These results highlight a potentially powerful approach for the design and synthesis of efficient and durable electrocatalysts for HER.