Current Oscillations in the Course of Birnessite Electrodeposition as Related to Resulting Microstructure: Experimental Manifestations and Qualitative Hypotheses | Sciact - CRIS-system of Boreskov Institute of Catalysis

Current Oscillations in the Course of Birnessite Electrodeposition as Related to Resulting Microstructure: Experimental Manifestations and Qualitative Hypotheses Full article

Journal

Journal of Solid State Electrochemistry
ISSN: 1432-8488 , E-ISSN: 1433-0768

Output data

Year: 2024, Volume: 28, Pages: 1705–1717 Pages count : 13 DOI: 10.1007/s10008-023-05626-3

Tags

Deposits; Diffusion; Electrodes; Microstructure

Authors

Pugolovkin Leonid V. ¹ , Levin Eduard E. ^1,2 , Arkharova Natalya A. ² , Orekhov Anton S. ² , Presnov Denis E. ^3,4 , Cherstiouk Olga V. ^5,6 , Tsirlina Galina A. ^1,7

Affiliations

1	Department of Electrochemistry, Faculty of Chemistry, M.V. Lomonosov Moscow State University, Moscow, Russia
2	FSRC “Crystallography and Photonics” RAS, Leninsky Prospekt 59, 119333 Moscow, Russia
3	Skobeltsyn Institute of Nuclear Physics, M.V. Lomonosov Moscow State University, Moscow, Russia
4	Cryoelectronics” Laboratory, Faculty of Physics, M.V. Lomonosov Moscow State University, Moscow, Russia
5	G.K. Boreskov Institute of Catalysis, SB RAS, Novosibirsk, Russia
6	Novosibirsk State University, Novosibirsk, Russia
7	Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMI, Grenoble, France

Funding (1)

Russian Foundation for Basic Research

18-29-12064 (АААА-А18-118080390016-1)

We report oscillations of current which accompany anodic deposition from Mn(II) solutions in a neutral acetic buffer and also cathodic birnessite deposition from alkaline permanganate solutions. We demonstrate that for both processes, oscillations appear at high enough overpotentials. The current oscillations are affected by solution convection. The results of rotating disc electrode experiments favor mixed control, with higher diffusion contribution in case of cathodic deposition. Electron microscopy combined with electron and X-ray diffraction and coulometric analysis is applied to assign oscillations to certain morphological features of the deposits. A pronounced difference in microstructure is found for anodic and cathodic deposits formed under oscillating growth conditions: “anodic” birnessite consists of parallel layers of small crystals, whereas “cathodic” birnessite is globular. This difference is interpreted with account for specific crystallographic features. Namely, the more ordered birnessite lattice formed by reduction of permanganate favors a preferentially lateral growth of thin lamellas, in contrast to birnessite having a pronounced interplane distortion, formed in the course of anodic deposition. We assign the periodic current decrease to diffusion limitations in growing porous layers and assume that the subsequent current increase in each period corresponds to dendrite-like growth of a low number of crystals located in the outer diffusion layer.

Pugolovkin L.V. , Levin E.E. , Arkharova N.A. , Orekhov A.S. , Presnov D.E. , Cherstiouk O.V. , Tsirlina G.A.
Current Oscillations in the Course of Birnessite Electrodeposition as Related to Resulting Microstructure: Experimental Manifestations and Qualitative Hypotheses
Journal of Solid State Electrochemistry. 2024. V.28. P.1705–1717. DOI: 10.1007/s10008-023-05626-3 WOS Scopus РИНЦ AN OpenAlex

Submitted:	Jun 27, 2023
Accepted:	Jul 30, 2023
Published online:	Sep 9, 2023
Published print:	May 1, 2024

Web of science:	WOS:001065104600003
Scopus:	2-s2.0-85170070893
Elibrary:	61739373
Chemical Abstracts:	2023:1881826
OpenAlex:	W4386571535

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