The excitation of surface plasmons (SPs) — collective oscillation of conduction-band electrons in nanostructures — can afford photon, electron and heat energy redistribution over time and space. Making use of this ability, plasmon-enhanced molecular spectroscopy (PEMS) techniques with ultra-high sensitivity and surface selectivity have attracted much attention and have undergone considerable development over the past four decades. Recently, the development of plasmon-mediated chemical reactions (PMCRs) has shown the potential to have a large impact on the practice of chemistry. PMCRs exhibit some obvious differences from and potential advantages over traditional thermochemistry, photochemistry and photocatalysis. However, our physicochemical understanding of PMCRs is still far from complete. In this Review, we analyse the similarities and distinctive features of PEMS and PMCRs and compare PMCRs with traditional photochemical and thermochemical reactions. We then discuss how PMCRs can be improved by rationally designing and fabricating plasmonic nanostructures, selecting suitable surface and interface mediators and teaming them synergistically.

表面等离子体激元（SPs）的激发-纳米结构中导带电子的集体振荡-可以使光子，电子和热能随时间和空间重新分布。利用这种能力，具有超高灵敏度和表面选择性的等离激元增强分子光谱技术（PEMS）在过去的40年中引起了人们的广泛关注并取得了长足的发展。最近，等离激元介导的化学反应（PMCR）的发展已显示出对化学实践产生巨大影响的潜力。与传统的热化学，光化学和光催化相比，PMCR具有明显的区别和潜在的优势。但是，我们对PMCR的理化理解还远远不够。在这篇评论中，我们分析了PEMS和PMCR的相似性和鲜明特征，并将PMCR与传统的光化学和热化学反应进行了比较。然后，我们讨论了如何通过合理设计和制造等离激元纳米结构，选择合适的表面和界面介体并协同合作来改善PMCR。