Key Takeaways & Executive Findings
- •• • Ru/ReS2 heterostructure achieves an overpotential of 47 mV at 10 mA cm−2 in acidic HER, outperforming Pt/C (54 mV) and many reported Ru-based catalysts, indicating superior intrinsic activity. • • Tafel slope of 38 mV dec−1 for Ru/ReS2 suggests a Volmer-Heyrovsky mechanism with rapid kinetics, crucial for high-current-density operation in industrial electrolyzers. • • Exceptional durability: after 10,000 CV cycles, Ru/ReS2 shows negligible overpotential increase, whereas Pt/C degrades by ~54 mV, demonstrating long-term operational stability essential for commercial viability. • • The d-p coupling between Ru and ReS2 optimizes ΔG_H* and water adsorption, as confirmed by DFT, providing a design principle for enhancing HER performance in TMD-based catalysts.
Abstract
Green hydrogen production via electrocatalytic water splitting is pivotal for sustainable energy, yet the high cost and scarcity of platinum (Pt) catalysts impede large-scale adoption. Ruthenium (Ru)-based materials emerge as promising alternatives, but their performance requires enhancement. Two-dimensional transition metal dichalcogenides (TMDs), particularly ReS2, offer intrinsic 1T' phase with good conductivity and stability, yet suffer from inert surfaces limiting water adsorption. Here, we report a heterostructure comprising Ru nanoclusters anchored on ReS2 nanosheets (Ru/ReS2) to modulate electronic structure via d-p coupling. This design enhances water dissociation kinetics and optimizes hydrogen adsorption free energy (ΔG_H*). The Ru/ReS2 catalyst exhibits superior hydrogen evolution reaction (HER) activity in acidic media, achieving an overpotential of 47 mV at 10 mA cm−2 and a Tafel slope of 38 mV dec−1, outperforming commercial Pt/C (overpotential 54 mV, Tafel slope 45 mV dec−1). Notably, it demonstrates exceptional stability, with negligible degradation after 10,000 cyclic voltammetry cycles, contrasting with Pt/C's 54 mV overpotential increase. Density functional theory calculations reveal that d-p coupling between Ru and ReS2 optimizes the electronic structure, facilitating water adsorption and dissociation. This work provides a rational strategy for designing efficient, durable, and cost-effective HER electrocatalysts for green hydrogen production.
1. Introduction
The escalating demand for green hydrogen as a clean energy carrier has intensified research into efficient and cost-effective electrocatalysts for the hydrogen evolution reaction (HER). Platinum (Pt)-based materials remain the benchmark due to their near-zero overpotential, but their high cost and scarcity hinder large-scale deployment. Ruthenium (Ru) offers a more abundant and less expensive alternative, yet its catalytic activity and stability require improvement. Two-dimensional transition metal dichalcogenides (TMDs) like MoS2 have been extensively studied, but their semiconducting 2H phase suffers from poor conductivity and metastability of the conductive 1T' phase. ReS2, however, intrinsically adopts a stable 1T' structure with good conductivity, making it a promising support. Nevertheless, ReS2's inert basal plane limits water adsorption, a critical step in acidic HER. Thus, engineering ReS2 to enhance water dissociation while maintaining its structural integrity is a key challenge.
This work addresses this bottleneck by constructing a heterostructure of ruthenium nanoclusters on ReS2 nanosheets (Ru/ReS2). The d-p orbital coupling between Ru and ReS2 modulates the electronic structure, optimizing the adsorption energies of water and hydrogen intermediates. This synergistic effect accelerates the Volmer step, which is rate-limiting on pristine ReS2, leading to significantly improved HER kinetics. The Ru/ReS2 catalyst demonstrates an overpotential of 47 mV at 10 mA cm−2 and a Tafel slope of 38 mV dec−1, surpassing Pt/C and many previously reported Ru-based catalysts. Moreover, it exhibits outstanding stability over 10,000 cycles, addressing the durability concerns of Ru-based systems. This strategy offers a pathway to design efficient, stable, and cost-effective HER electrocatalysts for green hydrogen production.
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Lei Wang, Ruolin Guo, Mengjie Liu, Zhenzhen Zheng, Yue Geng, Zhi Chen, Guoqiang Li, Hao Lin, Jiajun Chen, Chunli Wang, Dianhong Wang, Menghao Guo, Xiaolong Zhu, Yifan Yu, Jiacheng Jayden Wang, Hongji Yu, Wei Zhao, Zhangliu Tian, Jinxing Mi, Kai Huang, Liangzhu Zhang (2026). Electronic regulation via d-p coupling between ruthenium nanoclusters and ReS2 nanosheets for enhanced green hydrogen production performance. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-026-4181-6
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Frequently Asked Questions
What is the specific overpotential and Tafel slope of the Ru/ReS2 catalyst, and how do they compare to Pt/C under identical conditions?
The Ru/ReS2 catalyst exhibits an overpotential of 47 mV at a current density of 10 mA cm−2, which is lower than Pt/C's 54 mV. The Tafel slope is 38 mV dec−1, compared to Pt/C's 45 mV dec−1, indicating faster reaction kinetics.
How does the d-p coupling between Ru and ReS2 enhance the HER activity, and what is the underlying mechanism?
Density functional theory (DFT) calculations reveal that d-p coupling between Ru and ReS2 modulates the electronic structure, optimizing the adsorption free energy of hydrogen (ΔG_H*) and facilitating water dissociation. This lowers the energy barrier for the Volmer step, which is rate-limiting on pristine ReS2, thereby enhancing HER kinetics.
What is the long-term stability of Ru/ReS2 under continuous operation, and how does it compare to Pt/C?
After 10,000 cyclic voltammetry (CV) cycles, Ru/ReS2 shows negligible increase in overpotential, whereas Pt/C experiences an increase of approximately 54 mV. This indicates superior durability of Ru/ReS2, which is critical for practical electrolyzer applications.
What is the significance of using ReS2 over other TMDs like MoS2 in this heterostructure?
ReS2 intrinsically adopts a stable 1T' phase with good electrical conductivity, avoiding the phase transition issues seen in MoS2 (from 1T' to 2H). This stability ensures consistent catalytic performance and enhances electron transfer, contributing to the improved HER activity.
What are the potential scalability and cost implications of Ru/ReS2 for industrial green hydrogen production?
Ru is more abundant and less expensive than Pt, and ReS2 can be synthesized via scalable methods. The high activity and stability of Ru/ReS2 could reduce the catalyst loading required, lowering overall system costs. However, further studies on large-scale synthesis and electrode fabrication are needed to assess industrial feasibility.
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