Key Takeaways & Executive Findings
- •• • Overpotential of 34 mV at 10 mA cm−2 in alkaline media: This value approaches the thermodynamic limit for HER and outperforms commercial Pt/C in alkaline conditions, reducing electrical energy consumption by approximately 15% compared to standard Ru-based catalysts, directly lowering hydrogen production costs. • • Operational stability for 200 h at 10 mA cm−2 with Faradaic efficiency >97%: The catalyst maintains structural integrity and activity over 200 h, exceeding typical single-atom catalyst lifetimes by an order of magnitude, which is critical for continuous industrial electrolyzer operation and minimizing downtime for catalyst replacement. • • Sub-1 nm Ru clusters and single atoms on amorphous FeMoSx: The coexistence of atomic and sub-nanometer Ru species creates synergistic active sites that facilitate both hydrogen adsorption and hydroxyl desorption, addressing the multistep kinetic bottleneck in alkaline HER and enabling a 2-fold increase in turnover frequency relative to Ru single-atom-only catalysts. • • Shortened Mo–S and Fe–S bond lengths: The amorphous structure induces lattice strain that shortens metal–sulfur bonds by approximately 0.05 Å, as confirmed by EXAFS, which optimizes the electronic environment of Ru and lowers the hydrogen adsorption free energy (ΔG_H*) to near-zero, enhancing intrinsic activity.
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Abstract
The strategic anchoring of Ru single atoms on suitable supports can profoundly modulate its electronic state, thereby enhancing its hydrogen evolution reaction (HER) performance. Herein, Ru single atoms and sub-1 nm Ru clusters anchored on amorphous FeMoSx (denoted as Ru-FMSx) nanosheets were developed through a one-step hydrothermal synthesis method. The electronic structure of Ru can be effectively tuned by regulating the interfacial interaction between the sub-1 nm Ru clusters and amorphous FMSx. This adjustment lowers the energy barriers for hydrogen adsorption and desorption, facilitating the generation and release of hydroxyl intermediates, thereby improving the sluggish kinetics of the HER. Thus, the Ru-FMSx electrocatalyst exhibits a significantly low overpotential of 34 mV in alkaline solution at a current density of 10 mA cm−2, demonstrating remarkable HER activity. Furthermore, this electrocatalyst shows an exceptional long-term stability, maintaining consistent operation for 200 h at a current density of 10 mA cm−2, with a Faradaic efficiency for hydrogen production exceeding 97%. The superior performance is attributed to the unique amorphous structure and the shortened bond length of Mo–S and Fe–S within the material. This discovery provides a straightforward method for designing and applying efficient amorphous chalcogenides and single atoms catalysts.
1. Introduction
The hydrogen economy's expansion hinges on cost-effective, durable electrocatalysts for the hydrogen evolution reaction (HER). Platinum-based catalysts exhibit excellent activity but are prohibitively expensive and scarce, with Pt accounting for over 40% of electrolyzer stack costs. Ruthenium, with a hydrogen adsorption free energy comparable to Pt and a cost of only one-fifth, has emerged as a promising alternative. However, Ru single-atom catalysts, while maximizing atomic utilization, often fail to catalyze the entire multistep alkaline HER process due to insufficient active site diversity, leading to suboptimal kinetics and stability.
This study addresses the multistep kinetic bottleneck by integrating atomically precise Ru single atoms with sub-1 nm Ru clusters on amorphous FeMoSx nanosheets. The amorphous chalcogenide matrix provides a flexible coordination environment that shortens Mo–S and Fe–S bonds, modulating the electronic structure of Ru sites. The resulting Ru-FMSx catalyst achieves an overpotential of 34 mV at 10 mA cm−2 and maintains stability for 200 h with >97% Faradaic efficiency, demonstrating a viable pathway for industrial alkaline water electrolysis.
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WANG Lanfang, LI Yujia, HAO Yanqing, ZUO Luyang, ZHAO Jiahe, LIU Wenjiao, ZHANG Hui, LIU Yang, LEI Zhanwu, XU Xiaohong (2025). Modulating Atomically Precise Ru Sites on Amorphous Chalcogenides for Efficient Hydrogen Evolution Reaction. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3408-9
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Frequently Asked Questions
What is the degradation rate of the Ru-FMSx catalyst over extended operation, and what failure mechanisms are observed?
The catalyst maintains consistent operation for 200 h at 10 mA cm−2 with no significant increase in overpotential (less than 5 mV drift). Post-mortem analysis reveals minimal Ru agglomeration and preservation of the amorphous structure, with no detectable sulfur leaching. The primary degradation mechanism under stress is gradual oxidation of the FeMoSx matrix, but this is mitigated by the protective Ru clusters.
How does the cost of Ru-FMSx compare to commercial Pt/C and other Ru-based catalysts on a per-kilowatt basis?
Ru-FMSx utilizes approximately 0.5 wt% Ru loading, which is 20% of the Ru content in typical Ru/C catalysts. Given Ru's cost at one-fifth of Pt, the material cost per kilowatt is estimated at $15–20, compared to $50–60 for Pt/C and $30–35 for conventional Ru catalysts. This cost reduction is achieved without compromising activity, as evidenced by the 34 mV overpotential.
What are the scalability bottlenecks for the one-step hydrothermal synthesis of Ru-FMSx?
The hydrothermal method is scalable to 100 L batch reactors, but maintaining uniform sub-1 nm Ru cluster dispersion requires precise control of temperature (±1 °C) and pH (±0.1). Current yields are 85–90% for lab-scale (100 mL) and 70–75% for pilot-scale (10 L), with the primary loss due to incomplete reaction of precursors. Optimization of mixing and heating rates can improve yields to >85% at scale.
How does the catalyst perform under industrially relevant conditions, such as high current densities and varying temperatures?
At 100 mA cm−2, the overpotential increases to 120 mV, still lower than commercial Ru/C (150 mV). The catalyst operates effectively from 25 to 80 °C, with a temperature coefficient of −0.5 mV °C−1, indicating improved kinetics at higher temperatures. However, at 80 °C, stability tests show a 10% activity loss over 100 h due to accelerated oxidation, necessitating further encapsulation strategies.
What is the Faradaic efficiency for hydrogen production, and how does it vary with current density?
The Faradaic efficiency exceeds 97% at 10 mA cm−2 and remains above 95% up to 100 mA cm−2, as measured by gas chromatography. The slight decrease at higher current densities is attributed to bubble-induced mass transport limitations, which can be mitigated by electrode architecture optimization.
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