2019
DOI: 10.1002/celc.201901415
|View full text |Cite
|
Sign up to set email alerts
|

Models and Their Limitations in the Voltammmetric Parameterization of the Six‐Electron Surface‐Confined Reduction of [PMo12O40]3− at Glassy Carbon and Boron‐Doped Diamond Electrodes

Abstract: In acidic media, three well-defined surface confined overall two electron transfer reactions derived from closely spaced oneelectron steps are observed in the DC and AC voltammetry of ½PMo 12 O 40 � 3À . In this study, parameterization of these processes by sinusoidal AC voltammetry at glassy carbon (GC) and boron doped diamond (BDD) electrodes has been undertaken in 1 M HClO 4 . The experiment-simulation comparison of even a simplified reaction scheme required estimation of 21 parameters, which is an exceptio… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1
1

Citation Types

3
9
0

Year Published

2020
2020
2022
2022

Publication Types

Select...
6

Relationship

3
3

Authors

Journals

citations
Cited by 13 publications
(12 citation statements)
references
References 40 publications
(94 reference statements)
3
9
0
Order By: Relevance
“…The acid dependence and simulation details for this and related polyoxometalates have been reviewed ( Bond, 2002 ). A fully analogous situation to the present study ( Robinson et al, 2018 ; Robinson et al, 2019 ) has been demonstrated to apply for surface confined reduction of [PMo 12 O 40 ] 3- ; in highly acid media it is shown to be well modelled by treatment as two closely spaced one-electron reduction steps rather than a simultaneous two-electron reduction processes. Conversely, more exotic electron-proton transfer schemes like the elegant “wedge” scenario are necessary for describing electron and proton transfer via an intermediate H-bond complex in some organic molecules ( Clare et al, 2019 ).…”
Section: Discussionsupporting
confidence: 62%
See 1 more Smart Citation
“…The acid dependence and simulation details for this and related polyoxometalates have been reviewed ( Bond, 2002 ). A fully analogous situation to the present study ( Robinson et al, 2018 ; Robinson et al, 2019 ) has been demonstrated to apply for surface confined reduction of [PMo 12 O 40 ] 3- ; in highly acid media it is shown to be well modelled by treatment as two closely spaced one-electron reduction steps rather than a simultaneous two-electron reduction processes. Conversely, more exotic electron-proton transfer schemes like the elegant “wedge” scenario are necessary for describing electron and proton transfer via an intermediate H-bond complex in some organic molecules ( Clare et al, 2019 ).…”
Section: Discussionsupporting
confidence: 62%
“…Other researchers have published work on the experimental measurement and theoretical modelling of solution phase voltammetry of such electrochemical-electrochemical stepwise multiple electron transfer processes ( Evans, 2008 ; Lopez-Tenes et al, 2014 ). We, and others, have published a number of analogous studies on surface confined species such as the H2ase-MFHypD system we describe here ( Finklea, 2001 ; Lee et al, 2011 ; Stevenson et al, 2012 ; Robinson et al, 2018 ; Robinson et al, 2019 ).…”
Section: Methodsmentioning
confidence: 99%
“…Data optimisation based on total current and harmonic percentage has been successfully employed in previous studies. [15,16,[44][45][46] Thus, as expected, the TCDS objective function provides an excellent fit to the synthetic data and excellent recovery for all parameters. On the other hand, the MLE-TCDS objective function slightly overestimates the faradaic component parameters and underestimates the non-faradaic capacitance ones as shown in Figures 3a, 3c, 3d, even for this simplest possible scenario where the double layer capacitance is simulated and fitted as a potential independent constant (c 0 ).…”
Section: Comparison Of Data Analysis Methods Using Synthetic Datasupporting
confidence: 73%
“…PINTS has been used previously to fit synthetic and experimental total current AC voltammetric data. [15,16,[44][45][46] However, a major advantage of large amplitude AC voltammetry, not available in the total current method, is access to resolved harmonics at integer multiples of the frequency of the applied sine wave. These harmonics provide variable levels of sensitivity to some of the parameters of interest in this study.…”
Section: Maximum Likelihood Estimated Total Current Difference Squaredmentioning
confidence: 99%
“…The optimisation approach gives, at least for well-posed problems with close to perfect models, the globally optimal solution for the parameters of interest, but generally gives only point estimates of the parameter values. Parameterisation of over 20 variables from a single data set has been achieved using this approach [30].…”
mentioning
confidence: 99%