Nanoplasmonics is currently experiencing an ongoing renaissance as a result of the booming research interest in LSPR-mediated but semiconductor-free photocatalysis and photoelectrochemistry directly over nanometals with excellent catalytic activity and conductive properties. To shed light on the underlying mechanism, the present study puts forward H₂O₂ as the probe molecule, with which the electroreduction at the phase boundary with photoexcited Ag nanowires (NWs) was systemically investigated. In particular, the reaction rate depends not only linearly on the illumination intensity but also on the resonant wavelength of the characteristic LSPR of the Ag NWs, evidently illustrating that the photoelectrochemical H₂O₂ reduction is mediated by the LSPR-induced energetic electrons of the Ag NWs. In addition to the mechanistic insights, the present study further highlights the great promise of such semiconductor-free LSPR-mediated photoelectrochemistry of H₂O₂ over Ag NWs in the analytical biochemistry field via proof-of-concept solar photoelectrochemical detection of ultradiluted H₂O₂ in PBS. The Ag NWs deposited on a carbon cloth substrate as the working electrode exhibit excellent sensitivity amounting to 118 μA cm⁻² mM⁻¹ under solar illumination, well outperforming that of the electrochemical counterpart measured in the dark by 50%.

由于对具有优异的催化活性和导电性能的LSPR介导的但无半导体的光催化作用和光电化学作用的直接研究兴趣越来越高，因此，纳米等离子体技术正经历着持续的复兴。为了阐明其潜在机理，本研究提出了H ₂ O ₂作为探针分子，利用该分子系统研究了光激发Ag纳米线（NWs）在相界处的电还原。特别地，反应速率不仅线性地依赖于照明强度，而且还依赖于Ag NWs的特征LSPR的共振波长，这显然表明光电化学H ₂ O ₂还原是由LSPR诱导的Ag NWs的高能电子介导的。除了机理上的见解之外，本研究还通过概念验证太阳光电化学检测超稀释H _2的方法，进一步强调了在分析生物化学领域中这种无半导体的LSPR介导的H ₂ O ₂在Ag NWs上的光电化学的巨大前景。PBS中的O ₂。沉积在作为工作电极的碳布基材上的Ag NW在太阳光下显示出极好的灵敏度，达到118μAcm ^-2  mM ^-1，比在黑暗中测得的电化学对应物的灵敏度高出50％。