基于这些研究，我们在此提出假设：通过等离子体纳米粒子的局域表面等离子体共振（LSPR）将含氧中间体限制在活性位点周围，这些积累的中间体可作为光驱动的溢出位点，与催化剂表面直接相互作用（图1b）。我们验证了一种等离子体驱动的中间体溢出策略，其中析出的银纳米颗粒的局域表面等离子体共振（LSPR）引导氢氧根离子瞬时化学吸附促进剂（ICPH）靠近催化活性位点。通过利用Sr₀.₉₅Ag₀.₀₅Nb₀.₁Co₀.₉O₃-d纳米纤维（p-SANC NF）表面的自重组等离子体纳米颗粒， 我们观察到，通过与银表面的氢氧根离子溢出效应，氧化还原反应（ORR）和氧化电解（OER）过程的氧气氧化还原电化学活性均显著增强，且该增强效应超越了银的理论可逆过电位极限（约0.7 eV）。这种增强效应发生于LSPR条件下，当ICPH在催化活性位点附近生成时。此外，通过等离子体锌空气电池及时间分辨X射线吸收光谱测量，我们揭示了LSPR条件下动态的局部ICPH及电子重分布过程。值得注意的是，在等离子体条件下，p-SANC NF 中 Co 位点的 3d 电子填充会立即重构为低 d 带电子占据，在放电过程中平均为 d−0.135，在充电过程中平均为 d−0.19。与传统电催化相比，电催化剂的等离子体激发使 ORR 的催化活性提高了 2.6 倍，OER 的催化活性提高了 4.6 倍，同时抑制了不希望产生的 H2O2（约 7%）。在等离子体辅助的锌空气电池中，p-SANC NF催化剂在高电流密度（50 mA cm⁻²）下，无论是ORR还是OER，其过电位均较低，ΔE = 0.76 V，而最先进的Pt/C + RuO₂催化剂的ΔE为1.12 V。与传统的基于材料的双组分系统不同，这种等离子体增强的设计为诱导中间体溢出提供了一条动态途径，为克服多步电催化中的固有规模限制提供了一种有前景的策略。
Fig. 1. Schematic description of the reaction pathway on plasmon-driven electrochemical process. (a) Conventional material-based hybrid system for spillover, where the electrocatalyst is coupled with promoter materials to induce intermediate migration. (b) Plasmon-driven electrocatalyst system, in which localized surface plasmon resonance (LSPR) generates hot carriers that dynamically activate hydroxide adsorption promoters, enabling light-induced spillover to the catalytic interface. (c) The potential energy diagram of three different conditions for oxygen reduction reaction and oxygen evolution reaction pathway. (d) The theoretical overpotential based on Gibbs free energy of the rate-determining step for reversible oxygen electrochemical reaction. (e) The surface configuration at different reaction stages with/without hydroxide promoter driven by LSPR.
Fig. 2. Structural characterizations. SEM images (a) before exsolution and (b) after exsolution process. (c) Wavelet transform (WT) EXAFS of e-SANC NF and p-SANC NF samples along with reference samples at Ag K-edge. (d) Ag K-edge XANES spectra of e-SANC NF and p-SANC NF about Ag foil and AgO. (e) Fourier transform of k2-weighted EXAFS spectra of Ag K-edge. (f) XPS spectra of Ag 3d for e-SANC NF and p-SANC NF. (g) UV–vis absorption spectra of e-SANC NF and p-SANC NF.
Fig. 3. Bifunctional electrochemical (ORR and OER) performances and plasmonic enhancement factors. (a) Bifunctional oxygen electrocatalytic activities for each catalyst according to three-electrode system tests in O2 saturated with 0.1 M KOH electrolyte, and (b) the corresponding ORR and OER Tafel plots. (c) H2O2 selectivity for each catalyst with/without plasmonic excitation determined using the RRDE method. (d) plasmonic enhancement factors for both ORR, OER (bottom), and 4-electron pathway (upper). (e) Conditions for ORR and OER: current normalized by the geometric area of the electrode, a rotation rate of 1600 rpm, electrochemical surface area (ECSA) for each catalyst.
Fig. 4. Plasmoelectric performances of plasmonic-assisted aqueous Zinc-air batteries. (a) Schematic illustration of aqueous ZAB. (b) The open circuit voltage curves of ZAB with Pt/C+RuO2, p-SANC SP, and p-SANC NF with/without light irradiation. (c) Polarization and corresponding power density profiles of each catalyst. (d) Chronoamperometric profiles for discharge process at a different voltage ranging from 1.2 to 0.4 V. (e) Charge and discharge polarization curves. (f) Galvanostatic discharge-charge cycling performance of aqueous ZAB with Pt/C+RuO2 and SANC NF-AR catalyst with/without light irradiation at a constant current density of 50 mA cm−2. Chronopotentiometric charge–discharge test with 10-minute hold at each step. (g) Corresponding energy efficiency and coulombic efficiency under light irradiation. (h) Rechargeable ZAB performance chart, regarding voltage gap and current density for plasmonic ZAB under plasmonic condition (red colored star), ZAB under dark condition (black colored star) with p-SANC NF catalyst, and other reported ZABs.
Fig. 5. Operando XAFS spectra of Co K-edge under plasmon-assisted electrochemical conditions. (a) Operando Co K-edge XANES of p-SANC NF under different applied potentials with/without plasmonic condition, and ex-situ XANES spectra of the reference standards of Co foil, CoO, Co2O3, and Co3O4. The fitted average formal d-band electron counts of Co for p-SANC NF at different applied voltage (b) under dark condition, and (c) plasmonic condition. The operando XANES contour maps of Co as a function of different voltages in ZAB under dark condition (d), and plasmonic condition (e). (f) Differential Δμ XANES spectra obtained by subtracting the normalized spectrum at every potential to the spectrum recorded at 0.9 V in ZAB. (g) Differential Δμ XANES spectra between dark and plasmonic conditions at each potential. (h) The coverage of OHads corresponds to different voltage conditions with/without plasmonic conditions.本研究通过验证基于自重组等离子体纳米颗粒的等离子体驱动氢氧根离子化学吸附促进剂（ICPH）在Sr₀.₉₅Ag₀.₀₅Nb₀.₁Co₀.₉O₃-d纳米纤维（p-SANC NF）表面上的有效性，为可持续氧电催化领域带来了重大突破。在周围等离子体 Ag 纳米颗粒（既作为氢氧根离子的受体，也作为供体）上，LSPR 驱动的 ICPH 机制增强了反应动力学并改变了电化学路径，从而提高了 ORR 和 OER 的选择性，并降低了过电位。原位 X 射线吸收光谱和原位拉曼光谱揭示了氧化态中详细的电子和结构变化，放电期间 d 值下降 0.135，充电期间 d 值下降 0.19。综合来看，这些发现表明银（Ag）在向钴（Co）转移热空穴的同时，也充当了热电子的聚集位点，从而在等离子体条件下建立了一个动态的Ag–Co电荷转移通道，引导氢氧根溢出路径。这些变化由等离子体激发下Co位点上的OHads覆盖所驱动，突显了局域表面等离子体共振（LSPR）在氧电化学中的关键作用。采用等离子体驱动ICPH的水系锌空气电池在50 mA cm⁻²下实现了0.76 V的减小电压差（ΔE），具有高能量效率（约60%）和187 mW cm⁻²的功率密度，性能优于Pt/C和RuO₂催化剂（ΔE = 1.12 V， 117 mW cm⁻²)。此外，固态柔性锌空气电池中采用p-SANC NF（532 nm）时，其最大功率密度（54 mA cm⁻²下达38 mW cm⁻²）显著高于暗态条件（28 mW cm⁻²）及Pt/C+RuO₂体系（20.8 mW cm⁻²）。我们的研究结果凸显了等离子体驱动的ICPH作为光-物质耦合策略的潜力，可用于提升包括光辅助电化学平台在内的可持续能源系统的性能。该方法为改善氧气电催化提供了新的机理途径。
Jeongwon Kim, Linlin Cheng, Wen-Tse Huang, Chaozhen Liu, Yen-Huei Lin, Woo Jin Byun, Nur Aqlili Riana Che Mohamad, Jae Sung Lee, Feng Gong, Ru-Shi Liu, Dong Ha Kim, Yunfei Bu, Plasmon-driven oxygenated chemisorption acceleration of oxygen electrocatalysis for high-current cycling zinc-air batteries, Applied Catalysis B: Environment and Energy, 2026, https://doi.org/10.1016/j.apcatb.2026.126915
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