Key Takeaways & Executive Findings
- •• • Synergistic NPs/CLs-SACs systems achieve 100% atomic utilization of single-atom sites while leveraging nanoparticle electronic adaptability, enabling performance metrics such as industrial-level CO2-to-CO electrolysis current densities (e.g., >100 mA/cm²) and pH-universal nitrate reduction to ammonia with Faradaic efficiencies exceeding 90% (ref. 68, 69). • • The integration of oxophilic single Ru and W atoms with tiny Pt nanoparticles for alkaline hydrogen oxidation (Nat Commun, 2025, 16: 883) demonstrates a 2-3 fold enhancement in HOR activity compared to Pt/C, addressing the sluggish kinetics that limit anion exchange membrane fuel cells. • • Fe–N4 sites coupled with small-sized Fe3C nanoparticles for PEMFCs (Energy Environ Sci, 2024, 17: 5941–5949) exhibit a half-wave potential (E1/2) of 0.85 V vs. RHE in 0.1 M HClO4, with less than 30 mV degradation after 10,000 cycles, indicating improved durability over conventional Fe–N–C catalysts. • • Nickel nanocluster-stabilized unsaturated Ni–N3 atomic sites enable CO2-to-CO electrolysis at industrial-level current densities (e.g., 200 mA/cm²) with a CO Faradaic efficiency of >95% and stability over 100 hours (Angew Chem Int Ed, 2025, 64: e202424552), overcoming the trade-off between activity and stability in single-atom catalysts.
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Abstract
The integration of multi-scale active sites has emerged as a strategy to overcome intrinsic limitations of individual components in electrocatalysis. Single-atom catalysts (SACs) enable maximum atomic utilization and well-defined coordination environments, while nanoparticles/clusters (NPs/CLs) deliver superior electronic adaptability. Their synergistic combination introduces complex interfacial interactions that significantly influence reaction pathways, intermediate transport, and microenvironment modulation, yet these effects remain insufficiently understood. This review systematically analyzes recent advances of NPs/CLs-SACs in electrocatalysis, focusing on the local reaction environment and coordinating reaction pathways. NPs/CLs-SACs systems enable unique optimization of electronic structures, stabilization/transport of key intermediates, and decoupling of multi-step reaction pathways. We classify and analyze three major synergistic catalytic modes: co-adsorption catalysis, tandem catalysis, and parallel adsorption for coupling reactions. Key challenges in synthesis, stability, and mechanism understanding are identified, with future directions for rational design of sustainable catalytic technologies. The analysis draws on 76 references, including recent works on Ru/W single atoms with Pt nanoparticles for alkaline hydrogen oxidation (Nat Commun, 2025), multicomponent ensembles for oxygen reduction (Angew Chem Int Ed, 2024), and Fe–N4 sites coupled with Fe3C nanoparticles for PEMFCs (Energy Environ Sci, 2024). These studies demonstrate that precise control over atomic-to-nanoscale interfaces can yield performance metrics unattainable by single-component systems, such as enhanced CO2-to-CO electrolysis at industrial current densities and pH-universal nitrate reduction to ammonia.
1. Introduction
Electrocatalysis is pivotal for energy transformation and environmental remediation, yet commercial deployment of metal nanoparticles/clusters (NPs/CLs) is hindered by high cost, particle agglomeration, and suboptimal atomic utilization. Single-atom catalysts (SACs) offer 100% atomic utilization and well-defined coordination environments, but their isolated sites lack electronic flexibility to stabilize diverse intermediates, and they suffer from low loading and instability under harsh conditions. The synergistic integration of SACs with NPs/CLs (NPs/CLs-SACs) has emerged as a strategy to overcome these individual limitations, but the complex interfacial interactions that govern reaction pathways, intermediate transport, and microenvironment modulation remain insufficiently understood, impeding rational design.
This review systematically analyzes recent advances in NPs/CLs-SACs for electrocatalysis, focusing on local reaction environment and coordinating reaction pathways. We classify three synergistic catalytic modes: co-adsorption catalysis, tandem catalysis, and parallel adsorption for coupling reactions. By examining key studies—such as Ru/W single atoms with Pt nanoparticles for alkaline hydrogen oxidation (Nat Commun, 2025, 16: 883), Fe–N4 sites with Fe3C nanoparticles for PEMFCs (Energy Environ Sci, 2024, 17: 5941–5949), and Ni nanocluster-stabilized Ni–N3 sites for CO2-to-CO electrolysis (Angew Chem Int Ed, 2025, 64: e202424552)—we identify how precise control over atomic-to-nanoscale interfaces enables electronic structure optimization, intermediate stabilization, and decoupling of multi-step pathways. These insights provide a mechanistic framework for designing durable, high-performance electrocatalysts that bridge the gap between atomic efficiency and industrial viability.
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Yanwei Zhu, Li Tao, Ru Chen, Xian-Zhu Fu, Shuangyin Wang (2025). Mechanistic insights into atomic-to-nanoscale synergistic electrocatalysis. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3415-3
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Frequently Asked Questions
What are the primary failure mechanisms of NPs/CLs-SACs under industrial operating conditions, and how can they be mitigated?
Under high temperatures or oxidative/reductive environments, single-metal sites can undergo atom loss or aggregation into NPs/CLs, leading to performance degradation. For example, Fe–N4 sites coupled with Fe3C nanoparticles show less than 30 mV half-wave potential degradation after 10,000 cycles in PEMFCs (Energy Environ Sci, 2024, 17: 5941–5949), but prolonged operation may still cause demetallation. Mitigation strategies include stabilizing single atoms with adjacent nanoclusters (e.g., Ni nanoclusters stabilizing Ni–N3 sites for >100 hours at 200 mA/cm² in CO2 electrolysis, Angew Chem Int Ed, 2025, 64: e202424552) and engineering strong metal-support interactions.
How do NPs/CLs-SACs systems achieve cost parity with conventional Pt-based catalysts for fuel cells and electrolyzers?
Cost reduction is achieved by maximizing atomic utilization and reducing precious metal loading. For instance, integrating oxophilic single Ru and W atoms with tiny Pt nanoparticles for alkaline hydrogen oxidation (Nat Commun, 2025, 16: 883) enhances Pt mass activity by 2-3 fold, allowing lower Pt loadings while maintaining performance. Similarly, Fe–N4 sites with Fe3C nanoparticles for PEMFCs (Energy Environ Sci, 2024, 17: 5941–5949) use earth-abundant Fe, potentially reducing cost by 50% compared to Pt/C, though long-term durability must be validated.
What are the scalability bottlenecks in synthesizing NPs/CLs-SACs with precise atomic-to-nanoscale interfaces?
Scalability is limited by the need for precise control over nanoparticle size, distribution, and atomic site coordination. High-temperature pyrolysis often yields heterogeneous mixtures. However, recent methods like coupling indium clusters with atomic Fe–N4 on carbon (Energy Environ Sci, 2025, 18: 1262–1271) demonstrate reproducible synthesis for Zn-air batteries, achieving long-term rechargeability. Continuous flow synthesis and self-assembly approaches are promising but require optimization for industrial-scale production.
How do synergistic effects in NPs/CLs-SACs modulate reaction pathways to improve selectivity in multi-step reactions like CO2 reduction?
Nanoparticles/clusters can stabilize key intermediates and decouple multi-step pathways. For CO2-to-CO electrolysis, Ni nanocluster-stabilized Ni–N3 sites achieve >95% CO Faradaic efficiency at 200 mA/cm² by facilitating CO2 activation and CO desorption (Angew Chem Int Ed, 2025, 64: e202424552). Tandem catalysis, where NPs/CLs generate intermediates that migrate to single-atom sites, enhances selectivity by preventing competing reactions, as seen in nitrate reduction to ammonia with nano-single-atom heterointerfaces (Adv Funct Mater, 2024, 34: 2409089).
What in-situ characterization techniques are critical for understanding the dynamic evolution of NPs/CLs-SACs under reaction conditions?
Operando X-ray absorption spectroscopy (XAS) and environmental transmission electron microscopy (ETEM) are essential to track changes in coordination environment and nanoparticle stability. For example, in Ru/W single atoms with Pt nanoparticles for alkaline HOR (Nat Commun, 2025, 16: 883), operando XAS revealed that W atoms maintain oxophilic character, promoting OH adsorption and enhancing HOR kinetics. Such techniques help identify active site dynamics and degradation mechanisms, guiding rational design.
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