Jun Mei

Hydrogen spillover can decouple elementary steps in the hydrogen evolution reaction (HER), yet conventional bimetallic catalysts often suffer from discontinuous interfaces that block spillover pathways. Herein, an interfacial hydrogen spillover mechanism is engineered in a Pd–PdNi–Ni catalyst via a partial interface alloying strategy for pH‐universal hydrogen evolution. The graded PdNi interface serves as a recombination sink integrating two synergistic pathways: primary spillover, in which strongly adsorbed H* generated on Ni spontaneously migrates across the interface, and secondary spillover, in which H* produced on Pd also diffuses to the same interfacial sites. The dual spillover is driven by a favorable hydrogen intermediate gradient resulting from Ni‐to‐Pd electron transfer and an optimized d‐band center. The optimal catalyst delivers ultralow overpotentials of 60 mV (alkaline) and 37 mV (acidic) at 10 mA cm ⁻² , with robust durability, and the corresponding anion exchange membrane electrolyzer exhibits 1.73 V at 0.5 A cm ⁻² and 452 h stability in simulated seawater. Operando Raman spectroscopy detects Pd–H and Ni–H vibrations, providing direct evidence for hydrogen migration from both domains to the interface, and theoretical calculations confirm the electronic origin and spillover pathways. This work demonstrates a rational design for high‐performance HER catalysts by harnessing dual hydrogen spillover.

Hydrogen spillover can decouple elementary steps in the hydrogen evolution reaction (HER), yet conventional bimetallic catalysts often suffer from discontinuous interfaces that block spillover pathways. Herein, an interfacial hydrogen spillover mechanism is engineered in a Pd–PdNi–Ni catalyst via a partial interface alloying strategy for pH‐universal hydrogen evolution. The graded PdNi interface serves as a recombination sink integrating two synergistic pathways: primary spillover, in which strongly adsorbed H* generated on Ni spontaneously migrates across the interface, and secondary spillover, in which H* produced on Pd also diffuses to the same interfacial sites. The dual spillover is driven by a favorable hydrogen intermediate gradient resulting from Ni‐to‐Pd electron transfer and an optimized d‐band center. The optimal catalyst delivers ultralow overpotentials of 60 mV (alkaline) and 37 mV (acidic) at 10 mA cm ⁻² , with robust durability, and the corresponding anion exchange membrane electrolyzer exhibits 1.73 V at 0.5 A cm ⁻² and 452 h stability in simulated seawater. Operando Raman spectroscopy detects Pd–H and Ni–H vibrations, providing direct evidence for hydrogen migration from both domains to the interface, and theoretical calculations confirm the electronic origin and spillover pathways. This work demonstrates a rational design for high‐performance HER catalysts by harnessing dual hydrogen spillover.

Phosphorene represents a programmable two‐dimensional platform in which synthesis dictates molecular architecture, enabling precise control over ion transport and storage mechanisms. This review establishes a design‐centric framework by linking tailored synthesis strategies, from exfoliation to vapor‐phase growth, to the construction of phosphorene allotropes with targeted structural merits. It is demonstrated how this synthesis‐driven architecture directly governs ion transport kinetics and supports multifunctional roles of phosphorene as high‐capacity anodes, polysulfide‐trapping cathodes, solid‐electrolyte modifiers, or interfacial stabilizers across rechargeable battery and supercapacitors. Moreover, this review systematically correlates material states, including defective, doped, and heterostructured phosphorene, with tailored ion diffusion behaviors that govern electrochemical kinetics. Finally, critical challenges are thoroughly analyzed, and some forward‐looking research directions are outlined, emphasizing integrated strategies in material stabilization, interface engineering, and scalable synthesis to unlock full potential of phosphorene in powering next‐generation energy storage devices.

The sluggish kinetics of the urea oxidation reaction (UOR) are strongly associated with the high energy barriers required for the C‐N cleavage and N‐N coupling steps. While nickel‐based catalysts are promising, their performance is limited by high operational potentials and structural instability. This work introduces neodymium (Nd) as a Lewis acid site promoter into a nickel‐based framework to create Nd‐Ni oxide catalysts. The strong Lewis acidity of Nd centers enhances urea adsorption and facilitates C‐N cleavage and N‐N coupling, while the significant electronegativity difference between Nd and Ni induces electronic redistribution for optimizing intermediate adsorption for UOR. As a result, the optimal catalyst demonstrates superior UOR performance, in which a low potential of 1.347 V is required to achieve 10 mA cm ⁻² accompanied by excellent cycling stability. When integrated into a Zn‐urea battery, it delivers a peak power density of 11.6 mW cm ⁻² . This study highlights the critical role of Lewis‐acid engineering via rare‐earth metal incorporation in restructuring reaction pathways, and offers a promising strategy for advancing renewable energy conversion.

With the rapid development of renewable energy, electrocatalysis has assumed a central role in the conversion and storage of sustainable energy. Rare‐earth (RE) elements, characterized by their unique 4f electronic configurations, reversible multivalent states, and highly tunable physicochemical properties, offer a fundamentally distinct pathway for achieving precise control over catalyst electronic structures, interfacial chemistry, and reaction pathways. This review presents a comprehensive and mechanistic perspective on the distinctive, multi‐faceted roles of RE elements in advanced electrocatalysis. By systematically analyzing their intrinsic properties, the review elucidates the quantum‐chemical origins of their advantages in electronic structure modulation, stabilization of high‐energy intermediates, and enhancement of interfacial charge transport. Building upon these foundations, some major catalyst design strategies, encompassing atomic doping, defect engineering, nanostructuring, and interface construction, are critically summarized. Then, recent progress of RE‐based catalysts in various electrocatalytic reactions, including oxygen and hydrogen evolution, and carbon dioxide and nitrogen reduction reactions, are thoroughly reviewed to establish structure‐activity correlations. Finally, the review outlines future prospects and emerging frontiers in RE‐mediated catalysis, such as multi‐electron reaction pathway regulation and the construction of adaptive interfaces. This work aims to provide a fundamental understanding and strategic guidance for the rational design of efficient electrocatalysts enabled by RE elements.

Spillover phenomenon, which is characterized by the dynamic migration of active species across catalyst surfaces, provides a promising avenue to overcome the limitations dictated by the Sabatier principle in conventional catalysis. This comprehensive review highlights recent progress in multiplicate spillover, including hydrogen, oxygen, hydroxyl, and intermediate spillover, and their critical roles in modulating intermediate adsorption, strengthening interfacial transport, and manipulating catalytic dynamics. Then, various spillover‐mediated electrocatalytic reactions, such as hydrogen and oxygen evolution, carbon dioxide and nitrogen reduction, and methanol oxidization reactions, are systematically summarized. Finally, current challenges of different spillover systems are critically assessed and future research directions are briefly outlined. It is expected that this review offers some useful guidance on rational design of high‐performance spillover‐based electrocatalysts and promote advancement of sustainable energy conversion technologies.

The efficient production of hydrogen via acidic water electrolysis is hampered by the sluggish kinetics of the oxygen evolution reaction (OER) and the scarcity of robust bifunctional catalysts. Iridium‐based materials have been recognized as promising active sites; however, the atomic utilization should be maximized, and the stability requires further enhancement. This work introduces a support‐intensified catalyst design that features covalent Ir‐P‐Mo linkages for achieving robust water dissociation. Theoretical calculations reveal that the Ir─P─Mo bond enhances hydrogen evolution reaction (HER) activity by optimizing hydrogen adsorption, while the Ir─O─Mo bond is more favorable for OER. Guided by this principle, a catalyst with coexisting Ir‐O‐Mo and Ir‐P‐Mo linkages is rationally synthesized, which exhibits exceptional bifunctional performance in acid solution, including low overpotentials of 33 mV for HER and 249 mV for OER at 10 mA cm ⁻² . When configured in a symmetrical two‐electrode electrolyzer, it requires only 1.501 V to reach 10 mA cm ⁻² and demonstrates remarkable stability for 250 h with minimal voltage degradation. This work verifies the critical role of interfacial bond engineering in developing efficient and durable iridium‐based electrocatalysts for practical acidic water splitting.