Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche Université - CNRS N° 7591, Bâtiment Lavoisier, 15 rue Jean de Baïf, 75205 Paris Cedex 13, France.
J Am Chem Soc. 2015 Apr 29;137(16):5461-7. doi: 10.1021/jacs.5b00914. Epub 2015 Apr 21.
In relation to contemporary energy challenges, a number of molecular catalysts for the activation of small molecules, mainly based on transition metal complexes, have been developed. The time has thus come to develop tools allowing the benchmarking of these numerous catalysts. Two main factors of merit are addressed. One involves their intrinsic catalytic performances through the comparison of "catalytic Tafel plots" relating the turnover frequency to the overpotential independently of the characteristics of the electrochemical cell. The other examines the effect of deactivation of the catalyst during the course of electrolysis. It introduces the notion of the limiting turnover number as a second key element of catalyst benchmarking. How these two factors combine with one another to control the course of electrolysis is analyzed in detail, leading to procedures that allow their separate estimation from measurements of the current, the charge passed, and the decay of the catalyst concentration. Illustrative examples from literature data are discussed.
针对当代能源挑战，人们开发了许多用于小分子活化的分子催化剂，主要基于过渡金属配合物。因此，现在需要开发工具来对这些众多的催化剂进行基准测试。本文讨论了两个主要的评价标准。一个涉及通过比较与过电势无关的“催化塔菲尔图”来评估其内在催化性能，该图涉及到周转率与过电势的关系，而不考虑电化学池的特性。另一个则研究了催化剂在电解过程中失活的影响。它引入了极限周转率的概念，作为催化剂基准测试的第二个关键要素。这两个因素如何相互结合来控制电解过程，在详细分析之后，本文提出了从电流、电荷量和催化剂浓度衰减的测量中分别估算这两个因素的程序。文中还讨论了文献数据中的实例。
