Nair Akhil S, Anoop Anakuthil, Ahuja Rajeev, Pathak Biswarup
Department of Chemistry, Indian Institute of Technology Indore, Indore, Madhya Pradesh, India.
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, India.
J Comput Chem. 2021 Oct 15;42(27):1944-1958. doi: 10.1002/jcc.26725. Epub 2021 Jul 26.
Metal nanoclusters are an important class of materials for catalytic applications. Sub nanometer clusters are relatively less explored for their catalytic activity on account of undercoordinated surface structure. Taking this into account, we studied platinum-based sub nanometer clusters for their catalytic activity for oxygen reduction reaction (ORR). A comprehensive analysis with global optimization is carried out for structural prediction of the platinum clusters. The energetic and electronic properties of interactions of clusters with reaction intermediates are investigated. The role of structural sensitivity in the dynamics of clusters is unraveled, and unique intermediate specific interactions are identified. ORR energetics is examined, and exceptional activity for sub nanometer clusters are observed. An inverse size versus activity relationship is identified, challenging the conventional trends followed by larger nanoclusters. The principal role of atomicity in governing the catalytic activity of nanoclusters is illustrated. The structural norms governing the sub nanometer cluster activity are shown to be markedly different from larger nanoclusters.
金属纳米团簇是催化应用中的一类重要材料。由于表面结构配位不足，亚纳米团簇的催化活性相对较少被研究。考虑到这一点，我们研究了铂基亚纳米团簇对氧还原反应（ORR）的催化活性。通过全局优化对铂团簇的结构预测进行了全面分析。研究了团簇与反应中间体相互作用的能量和电子性质。揭示了结构敏感性在团簇动力学中的作用，并确定了独特的中间体特异性相互作用。研究了ORR能量学，并观察到亚纳米团簇具有异常活性。确定了尺寸与活性的反比关系，挑战了较大纳米团簇遵循的传统趋势。阐明了原子性在控制纳米团簇催化活性中的主要作用。结果表明，控制亚纳米团簇活性的结构规范与较大纳米团簇明显不同。
