Verma Rishi, Sharma Gunjan, Polshettiwar Vivek
Department of Chemical Sciences, Tata Institute of Fundamental Research, Mumbai, 400005, India.
Nat Commun. 2024 Sep 12;15(1):7974. doi: 10.1038/s41467-024-51916-3.
The debate surrounding the roles of thermal and non-thermal pathways in plasmonic catalysis has captured the attention of researchers and sparked vibrant discussions within the scientific community. In this review, we embark on a thorough exploration of this intriguing discourse, starting from fundamental principles and culminating in a detailed understanding of the divergent viewpoints. We probe into the core of the debate by elucidating the behavior of excited charge carriers in illuminated plasmonic nanostructures, which serves as the foundation for the two opposing schools of thought. We present the key arguments and evidence put forth by proponents of both the non-thermal and thermal pathways, providing a perspective on their respective positions. Beyond the theoretical divide, we discussed the evolving methodologies used to unravel these mechanisms. We discuss the use of Arrhenius equations and their variations, shedding light on the ensuing debates about their applicability. Our review emphasizes the significance of localized surface plasmon resonance (LSPR), investigating its role in collective charge oscillations and the decay dynamics that influence catalytic processes. We also talked about the nuances of activation energy, exploring its relationship with the nonlinearity of temperature and light intensity dependence on reaction rates. Additionally, we address the intricacies of catalyst surface temperature measurements and their implications in understanding light-triggered reaction dynamics. The review further discusses wavelength-dependent reaction rates, kinetic isotope effects, and competitive electron transfer reactions, offering an all-inclusive view of the field. This review not only maps the current landscape of plasmonic photocatalysis but also facilitates future explorations and innovations to unlock the full potential of plasmon-mediated catalysis, where synergistic approaches could lead to different vistas in chemical transformations.
围绕热途径和非热途径在等离子体催化中作用的争论引起了研究人员的关注，并在科学界引发了热烈的讨论。在这篇综述中，我们从基本原理出发，深入探索这一有趣的话题，最终详细理解不同的观点。我们通过阐明光照等离子体纳米结构中激发电荷载流子的行为来探究争论的核心，这是两种对立思想流派的基础。我们展示了非热途径和热途径支持者提出的关键论点和证据，呈现了他们各自立场的观点。除了理论分歧，我们还讨论了用于揭示这些机制的不断发展的方法。我们讨论了阿累尼乌斯方程及其变体的使用，阐明了随之而来的关于其适用性的争论。我们的综述强调了局域表面等离子体共振（LSPR）的重要性，研究了其在集体电荷振荡以及影响催化过程的衰减动力学中的作用。我们还探讨了活化能的细微差别，探究了其与温度和光强对反应速率依赖性的非线性之间的关系。此外，我们讨论了催化剂表面温度测量的复杂性及其在理解光触发反应动力学中的意义。综述进一步讨论了波长依赖性反应速率、动力学同位素效应和竞争性电子转移反应，提供了该领域的全面观点。这篇综述不仅描绘了当前等离子体光催化的格局，还促进了未来的探索和创新，以释放等离子体介导催化的全部潜力，其中协同方法可能会在化学转化中带来不同的前景。
