Solvent dynamical effects in electron transfer: electrochemical-exchange kinetics of sesquibicyclic hydrazines as a probe of coupled vibrational activation

1993 ◽  
Vol 97 (1) ◽  
pp. 181-188 ◽  
Author(s):  
Donald K. Phelps ◽  
Michael T. Ramm ◽  
Yichun Wang ◽  
Stephen F. Nelsen ◽  
Michael J. Weaver
1990 ◽  
Vol 112 (3) ◽  
pp. 1082-1088 ◽  
Author(s):  
Dabney White Dixon ◽  
Xiaole Hong ◽  
Scott E. Woehler ◽  
A. Grant Mauk ◽  
Bhavini P. Sishta

2011 ◽  
Vol 13 (37) ◽  
pp. 16530 ◽  
Author(s):  
Anja Wedig ◽  
Rotraut Merkle ◽  
Benjamin Stuhlhofer ◽  
Hanns-Ulrich Habermeier ◽  
Joachim Maier ◽  
...  

1978 ◽  
Vol 253 (10) ◽  
pp. 3702-3707
Author(s):  
B.E. Hedlund ◽  
P.E. Hallaway ◽  
B.E. Hallaway ◽  
E.S. Benson ◽  
A. Rosenberg

2021 ◽  
Author(s):  
Seyoung Kim ◽  
Sangho Lee ◽  
Soo-Hyung Choi ◽  
Kookheon Char

Author(s):  
Ruiyang Miao ◽  
Lidong Shao ◽  
Richard G. Compton

AbstractThe mechanism and kinetics of the electro-catalytic oxidation of hydrazine by graphene oxide platelets randomly decorated with palladium nanoparticles are deduced using single particle impact electrochemical measurements in buffered aqueous solutions across the pH range 2–11. Both hydrazine, N2H4, and protonated hydrazine N2H5+ are shown to be electroactive following Butler-Volmer kinetics, of which the relative contribution is strongly pH-dependent. The negligible interconversion between N2H4 and N2H5+ due to the sufficiently short timescale of the impact voltammetry, allows the analysis of the two electron transfer rates from impact signals thus reflecting the composition of the bulk solution at the pH in question. In this way the rate determining step in the oxidation of each specie is deduced to be a one electron step in which no protons are released and so likely corresponds to the initial formation of a very short-lived radical cation either in solution or adsorbed on the platelet. Overall the work establishes a generic method for the elucidation of the rate determining electron transfer in a multistep process free from any complexity imposed by preceding or following chemical reactions which occur on the timescale of conventional voltammetry.


2021 ◽  
Vol 11 (9) ◽  
pp. 3778
Author(s):  
Gene Yang ◽  
So-Yeun Kim ◽  
Changhee Sohn ◽  
Jong K. Keum ◽  
Dongkyu Lee

Considerable attention has been directed to understanding the influence of heterointerfaces between Ruddlesden–Popper (RP) phases and ABO3 perovskites on the kinetics of oxygen electrocatalysis at elevated temperatures. Here, we report the effect of heterointerfaces on the oxygen surface exchange kinetics by employing heteroepitaxial oxide thin films formed by decorating LaNiO3 (LNO) on La1.85Sr0.15CuO4 (LSCO) thin films. Regardless of LNO decoration, tensile in-plane strain on LSCO films does not change. The oxygen surface exchange coefficients (kchem) of LSCO films extracted from electrical conductivity relaxation curves significantly increase with partial decorations of LNO, whereas full LNO coverage leads to the reduction in the kchem of LSCO films. The activation energy for oxygen exchange in LSCO films significantly decreases with partial LNO decorations in contrast with the full coverage of LNO. Optical spectroscopy reveals the increased oxygen vacancies in the partially covered LSCO films relative to the undecorated LSCO film. We attribute the enhanced oxygen surface exchange kinetics of LSCO to the increased oxygen vacancies by creating the heterointerface between LSCO and LNO.


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