Plasmon-driven photocatalysis offers a unique means of leveraging nanoscale light–matter interactions to convert photon energy into chemical energy in a chemoselective and regioselective manner under mild reaction conditions. Plasmon-driven bond cleavage in molecular adsorbates represents a critical step in virtually all plasmon-mediated photocatalytic reactions and has been identified as the rate-determining step in many cases. This review article summarizes critical insights concerning plasmon-triggered bond-cleaving mechanisms gained through combined experimental and computational efforts over the past decade or so, elaborating on how the plasmon-derived physiochemical effects, metal–adsorbate interactions, and local chemical environments profoundly influence chemoselective bond-cleaving processes in a diverse set of molecular adsorbates ranging from small diatomic molecules to aliphatic and aromatic organic compounds. As demonstrated by several noteworthy examples, insights gained from fundamental mechanistic studies lay a critical knowledge foundation guiding rational design of nanoparticle–adsorbate systems with desired plasmonic molecule-scissoring functions for targeted applications, such as controlled release of molecular cargos, surface coating of solid-state materials, and selective bond activation for polymerization reactions.

中文翻译：

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等离激元驱动的分子切割


等离激元驱动的光催化提供了一种独特的方法，可以利用纳米级光-物质相互作用，在温和的反应条件下以化学选择性和区域选择性方式将光子能转化为化学能。分子吸附物中等离激元驱动的键裂解代表了几乎所有等离激元介导的光催化反应中的关键步骤，并且在许多情况下已被确定为速率决定步骤。这篇综述文章总结了过去十年左右通过实验和计算相结合工作获得的有关等离激元触发键切割机制的重要见解，详细阐述了等离激元衍生的理化效应、金属-吸附物相互作用和局部化学环境如何深刻影响从小双原子分子到脂肪族和芳香族有机物的各种分子吸附物中的化学选择性键切割过程化合物。正如几个值得注意的例子所证明的那样，从基础机理研究中获得的见解奠定了关键知识基础，指导合理设计具有所需等离子体分子剪刀功能的纳米粒子-吸附物系统，以实现目标应用，例如分子货物的受控释放、固态材料的表面涂层和聚合反应的选择性键活化。