Dual-Atom Catalysis for Oxygen Electrocatalysis

Oxygen electrocatalysis underpins key energy conversion technologies such as fuel cells, metal–air batteries and water‐splitting systems. Conventional precious‐metal catalysts deliver high activity but suffer from cost and scarcity. Dual‐atom catalysts (DACs) have emerged as a class of non‐precious electrocatalysts that bridge single‐atom and nanoparticle systems. By pairing two adjacent metal sites on tailored supports—often nitrogen‐doped carbon—DACs exploit synergistic electronic, geometric and spin interactions to modulate adsorption energies of oxygenated intermediates, activate O–O bonds via associative or dissociative pathways and facilitate the four‐electron reduction to water. Heteronuclear and homonuclear configurations enable fine‐tuning of reaction energetics, yielding half‐wave potentials and overpotentials comparable to or surpassing platinum benchmarks in both acidic and alkaline media. DACs have demonstrated multifunctional activity for both oxygen reduction and evolution reactions, high durability in metal–air cells and potential for solar‐driven hydrogen production. Key challenges remain in scalable synthesis of well‐defined diatomic sites, precise structural characterisation under operating conditions and comprehensive understanding of surface states. Progress in in situ diagnostics, theoretical modelling and advanced fabrication strategies continues to propel DACs towards practical deployment in sustainable energy technologies.

Research from Nature Portfolio

Recent studies have demonstrated that carefully engineered diatomic pairings can unlock superior oxygen reduction performance. One investigation placed atomically dispersed Fe–Mn pairs on a nitrogen‐doped carbon matrix and showed that Mn sites induce a spin‐state transition in adjacent Fe centres, optimising electronic coupling with O₂ and delivering half‐wave potentials of 0.928 V in alkaline and 0.804 V in acidic electrolytes. The catalyst exhibited durability and power density on par with commercial platinum in zinc–air batteries. Another report used an N-stripping and thermal-migration approach to convert cobalt nanoparticles sequentially into CoN₄ single atoms and then Co₂N₅ dual atoms. The resulting dual sites featured tailored spin states that balanced adsorption/desorption of intermediates, achieving outstanding multifunctional activity in both oxygen reduction and evolution reactions, stable zinc–air cycling for hundreds of hours and continuous solar‐driven hydrogen generation. A third work employed ab initio calculations to construct surface Pourbaix diagrams for various homonuclear and heteronuclear DACs, revealing that pre-adsorbed species and surface reconstructions at operating potentials can markedly alter active‐site properties. This finding underscores the necessity of evaluating actual surface states when interpreting catalytic activity.

Dual-Atom Catalysis for Oxygen Electrocatalysis publication trend

The graph below shows the total number of articles in dual-atom catalysis for oxygen electrocatalysis across all publications each year (not limited to Nature Index journals).

Technical terms

Dual-atom catalyst (DAC): Catalyst comprising two adjacent, atomically dispersed metal centres on a support, whose cooperative interactions enhance activity.

Oxygen reduction reaction (ORR): Electrochemical process reducing O₂ to H₂O or OH⁻ at the cathode, critical for fuel cells and metal–air batteries.

Oxygen evolution reaction (OER): Electrochemical oxidation of water to O₂ at the anode, essential for water splitting and rechargeable metal–air systems.

Half-wave potential: Electrode potential at which the current reaches half of its limiting diffusion value, used to gauge ORR activity.

Spin state: Distribution of unpaired electron spins in a transition metal centre, affecting orbital occupancy and catalytic behaviour.

Pourbaix diagram: Potential–pH map indicating stable surface species and phases under electrochemical conditions.

References

1. Current Status and Perspectives of Dual-Atom Catalysts Towards Sustainable Energy Utilization. Nano-Micro Letters (2024).
2. Regulating Fe-spin state by atomically dispersed Mn-N in Fe-N-C catalysts with high oxygen reduction activity. Nature Communications (2021).
3. Developing a class of dual atom materials for multifunctional catalytic reactions. Nature Communications (2023).
4. Surface states of dual-atom catalysts should be considered for analysis of electrocatalytic activity. Communications Chemistry (2023).
5. Direct Oxygen‐Oxygen Cleavage through Optimizing Interatomic Distances in Dual Single‐atom Electrocatalysts for Efficient Oxygen Reduction Reaction. Angewandte Chemie International Edition (2023).
6. Electron Modulation and Morphology Engineering Jointly Accelerate Oxygen Reaction to Enhance Zn‐Air Battery Performance. Advanced Science (2023).
7. In Situ X‐ray Absorption Spectroscopy of Metal/Nitrogen‐doped Carbons in Oxygen Electrocatalysis. Angewandte Chemie International Edition (2023).