Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion

Scientific Reports
Tatsuya ShinagawaKazuhiro Takanabe

Abstract

Microkinetic analyses of aqueous electrochemistry involving gaseous H2 or O2, i.e., hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are revisited. The Tafel slopes used to evaluate the rate determining steps generally assume extreme coverage of the adsorbed species (θ≈0 or ≈1), although, in practice, the slopes are coverage-dependent. We conducted detailed kinetic analyses describing the coverage-dependent Tafel slopes for the aforementioned reactions. Our careful analyses provide a general benchmark for experimentally observed Tafel slopes that can be assigned to specific rate determining steps. The Tafel analysis is a powerful tool for discussing the rate determining steps involved in electrocatalysis, but our study also demonstrated that overly simplified assumptions led to an inaccurate description of the surface electrocatalysis. Additionally, in many studies, Tafel analyses have been performed in conjunction with the Butler-Volmer equation, where its applicability regarding only electron transfer kinetics is often overlooked. Based on the derived kinetic description of the HER/HOR as an example, the limitation of Butler-Volmer expre...Continue Reading

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Citations

Dec 29, 2016·Journal of the American Chemical Society·Kyoungsuk JinKi Tae Nam
Jan 13, 2017·ACS Applied Materials & Interfaces·Jitang ChenQianwang Chen
Mar 30, 2017·Journal of the American Chemical Society·Andy I NguyenT Don Tilley
Apr 25, 2017·Journal of the American Chemical Society·Dong Young ChungYung-Eun Sung
Apr 25, 2017·Science Advances·Changdeuck BaeHyunjung Shin
Apr 5, 2017·Angewandte Chemie·Tran Ngoc HuanMarc Fontecave
Jan 14, 2017·Chemical Society Reviews·Nian-Tzu SuenHao Ming Chen
Jun 10, 2017·ACS Applied Materials & Interfaces·Ayon Karmakar, Suneel Kumar Srivastava
Jul 8, 2017·The Journal of Physical Chemistry Letters·Chunzhen YangAlexis Grimaud
May 29, 2018·Chemistry, an Asian Journal·Alam Venugopal Narendra KumarLiang Wang
Sep 5, 2017·Chemistry : a European Journal·Ferdinand HofAlain Pénicaud
Oct 3, 2017·ChemSusChem·Courtney A Downes, Smaranda C Marinescu
Sep 15, 2018·Chemical Communications : Chem Comm·Ziqiang WangXuping Sun

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