Issue 2, 2020

Electrodeposition behavior of homoleptic transition metal acetonitrile complexes interrogated with piezoelectric gravimetry

Abstract

Homoleptic acetonitrile complexes of first-row transition metal ions are a common product of the detrimental speciation of coordination complexes and organometallic compounds. However, the electrochemical properties of such species are mostly unknown, introducing ambiguities into interpretation of electroanalytical data associated with studies of molecular electrocatalysis. Here, we have cataloged the cyclic voltammetric properties of the solvento complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(I), and Zn(II) in acetonitrile electrolyte, providing information on the cathodic electrodeposition and anodic stripping processes occuring with each ion. The electrochemical quartz crystal microbalance (EQCM) has been used to quantify these processes, as well as the rates of the in situ corrosion of electrodeposited materials by the strong organic acid dimethylforamidinium, [DMFH]+. Ex situ X-ray photoelectron spectroscopic results confirm the interpretations of the voltammetric and gravimetric data, and confirm the periodic relationship between the metals. Taken together, the results described here provide an electrochemical roadmap useful in distinguishing currents arising from homogeneous electrocatalysis from currents associated with the redox cycling of secondary heterogeneous materials.

Graphical abstract: Electrodeposition behavior of homoleptic transition metal acetonitrile complexes interrogated with piezoelectric gravimetry

Supplementary files

Article information

Article type
Paper
Submitted
01 Okt 2019
Accepted
17 Nov 2019
First published
18 Nov 2019

Analyst, 2020,145, 466-477

Author version available

Electrodeposition behavior of homoleptic transition metal acetonitrile complexes interrogated with piezoelectric gravimetry

D. J. Sconyers and J. D. Blakemore, Analyst, 2020, 145, 466 DOI: 10.1039/C9AN01952A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements