Anantharaj Sengeni, Karthik Pitchiah Esakki, Noda Suguru
Department of Applied Chemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo, 169-8555, Japan.
Waseda Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo, 169-8555, Japan.
Angew Chem Int Ed Engl. 2021 Oct 18;60(43):23051-23067. doi: 10.1002/anie.202110352. Epub 2021 Sep 15.
For decades, turnover frequency (TOF) has served as an accurate descriptor of the intrinsic activity of a catalyst, including those in electrocatalytic reactions involving both fuel generation and fuel consumption. Unfortunately, in most of the recent reports in this area, TOF is often not properly reported or not reported at all, in contrast to the overpotentials at a benchmarking current density. The current density is significant in determining the apparent activity, but it is affected by catalyst-centric parasitic reactions, electrolyte-centric competing reactions, and capacitance. Luckily, a properly calculated TOF can precisely give the intrinsic activity free from these phenomena in electrocatalysis. In this Viewpoint we ask: 1) What makes the commonly used activity markers unsuitable for intrinsic activity determination? 2) How can TOF reflect the intrinsic activity? 3) Why is TOF still underused in electrocatalysis? 4) What methods are used in TOF determination? and 5) What is essential in the more accurate calculation of TOF? Finally, the significance of normalizing TOF by Faradaic efficiency (FE) is stressed and we give our views on the development of universal analytical tools to determine the exact number of active sites and real surface area for all kinds of materials.
几十年来,周转频率(TOF)一直是催化剂本征活性的准确描述符,包括涉及燃料生成和燃料消耗的电催化反应中的催化剂。不幸的是,与基准电流密度下的过电位相比,在该领域最近的大多数报告中,TOF往往没有得到正确报告或根本未被报告。电流密度在确定表观活性方面很重要,但它受到以催化剂为中心的寄生反应、以电解质为中心的竞争反应和电容的影响。幸运的是,正确计算的TOF可以精确地给出电催化中不受这些现象影响的本征活性。在本观点中,我们提出以下问题:1)是什么使得常用的活性标记物不适用于本征活性的测定?2)TOF如何反映本征活性?3)为什么TOF在电催化中仍未得到充分利用?4)TOF测定中使用了哪些方法?5)更准确计算TOF的关键是什么?最后,强调了通过法拉第效率(FE)对TOF进行归一化的重要性,并对开发通用分析工具以确定各种材料的活性位点的确切数量和真实表面积发表了我们的看法。