Controlling One-Electron vs Two-Electron Pathways in the Multi-Electron Redox Cycle of Nickel Diethyldithiocarbamate

Mazumder, Md. Motiur; Burton, Andricus; Richburg, Chase; Saha, Soumen; Cronin, Bryan T.; Duin, Evert C.; Farnum, Byron H.

doi:10.26434/chemrxiv.14725272.v1

Cited by 3 publications

(6 citation statements)

References 19 publications

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“…The oxidation reaction, first reported in the 1970's, 21,22 proceeds through an RSD/ECE mechanism described by eqs 2−5 and the green dashed line shown in Figure 3. 23,24 RSD refers to radical substrate dimerization, a term derived from 2e − electrochemistry with organic molecules, 18,25,26 which indicates that the chemical step involves reaction with a second equivalent of the substrate molecule (i.e., Ni II (dtc) 2 ). Following oxidation of Ni II (dtc) 2 to [Ni III (dtc) 2 ] + (eq 2), the chemical step involves ligand transfer from Ni II (dtc) 2 to [Ni III (dtc) 2 ] + (eq 3) to produce the trischelated Ni III (dtc) 3 , whereby it can be oxidized a second time (eq 4) or disproportionate (eq 5) to result in [Ni IV (dtc) 3 ] + .…”

Section: ■ Introductionmentioning

confidence: 99%

“…23,24 On the basis of the thermodynamic values for eqs 2−5, a reduction potential for eq 1 can be calculated to be E°(2e − ) = 0.02 V vs Fc +/0 . 23,24 The fact that 2e − reduction of [Ni IV (dtc) 3 ] + is not observed in MeCN suggests that the reverse reaction in eq 3 is kinetically slow. Therefore, efficient 2e − reduction requires rapid conversion from Ni III (dtc) 3 to [Ni III (dtc) 2 ] + .…”

Section: ■ Introductionmentioning

confidence: 99%

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Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi-Electron Storage in Redox Flow Batteries

et al. 2022

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Energy storage is a vital aspect for the successful implementation of renewable energy resources on a global scale. Herein, we investigated the redox cycle of nickel(II) bis-(diethyldithiocarbamate), Ni II (dtc) 2 , for potential use as a multielectron storage catholyte in nonaqueous redox flow batteries (RFBs). Previous studies have shown that the unique redox cycle of Ni II (dtc) 2 offers 2e − chemistry upon oxidation from Ni II → Ni IV but 1e − chemistry upon reduction from Ni IV → Ni III → Ni II . Electrochemical experiments presented here show that the addition of as little as 10 mol % Zn II (ClO 4 ) 2 to the electrolyte consolidates the two 1e − reduction peaks into a single 2e − reduction where [Ni IV (dtc) 3 ] + is reduced directly to Ni II (dtc) 2 . This catalytic enhancement is believed to be due to Zn II removal of a dtc − ligand from a Ni III (dtc) 3 intermediate, resulting in more facile reduction to Ni II (dtc) 2 . The addition of Zn II also improves the 2e − oxidation, shifting the anodic peak negative and decreasing the 2e − peak separation. H-cell cycling experiments showed that 97% Coulombic efficiency and 98% charge storage efficiency was maintained for 50 cycles over 25 h using 0.1 M Zn II (ClO 4 ) 2 as the supporting electrolyte. If Zn II (ClO 4 ) 2 was replaced with TBAPF 6 in the electrolyte, the Coulombic efficiency fell to 78%. The use of Zn II to increase the reversibility of 2e − transfer is a promising result that points to the ability to use nickel dithiocarbonates for multielectron storage in RFBs.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi-Electron Storage in Redox Flow Batteries

et al. 2022

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“…TBAPF 6 was recrystallized and dried by following the conventional method and preserved in a vacuum oven for further use. 18,19 0.1 M TBAPF 6 in acetonitrile was used as a solvent for cyclic voltammetry (CV) and battery experiments. The solution was degassed by nitrogen to remove the effect of oxygen on the redox properties of electrolytes.…”

Section: Chemicals and Instrumentmentioning

confidence: 99%

“…Some Ni and thiocarbamate-based complexes also showed a good possibility in NARFBs. 14,[16][17][18][19][20][21][22][23][24][25] However, to date, none of these complexes has fulfilled all the requirements. Acetyl ferrocene (AcFc) is a oneelectron system, which has a high solubility in MeCN at RT and 0 o C, high cyclic longevity, and can be used as catholyte in NARFBs.…”

Section: Introductionmentioning

confidence: 99%

Temperature-dependent study of AcFc-FeIII(acac)3 redox couple for non-aqueous redox flow battery

Mazumder

Islam

2022

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This article describes the temperature dependence electrochemical analysis of acetyl ferrocene (AcFc) and iron(III) acetylacetonate ([Fe(acac)3]) for non-aqueous redox flow batteries. An electrochemical cell consisting of AcFc and ([Fe(acac)3]) as catholyte and anolyte species, respectively, were constructed with a cell voltage of 1.41 V and Coulombic efficiencies >99% for up to 50 total cycles at 25o C (RT) and 0o C. Rotating ring disk electrode (RRDE) experiments suggest that diffusion coefficient decreases as the temperature decreases but overall storing capacity far better than aqueous redox flow battery (ARFBs). The electrochemical kinetic rate constant (k0) of AcFc was found larger than Fe(acac)3 but remains similar at both temperatures. NMR study shows no structural change in changing temperature and after battery experiments.

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“…17,19 Rapid kinetics associated with the chemical step is paramount to the observation of reversible The oxidation reaction, first reported in the 1970's 20,21 , proceeds through an RSD/ECE mechanism described by Equations 2-5 and the green dashed line shown in Figure 3. 22,23 RSD refers to radical substrate dimerization, a term derived from 2eelectrochemistry with organic molecules, 17,24,25 which indicates that the chemical step involves reaction with a second equivalent of the substrate molecule (i. (q, -CH2-), 1.21 (t, -CH3), UV-visible absorbance spectroscopy: λmax (ε) = 388 nm (5,600 M -1 cm -1 ) and 323 nm (26,700 M -1 cm -1 ), and X-ray crystallography.…”

Section: Introductionmentioning

confidence: 99%

A Zinc Catalyzed Two-Electron Nickel(IV/II) Redox Couple: New Catholyte Design for Redox Flow Batteries

Mazumder

Dalpati

Pokkuluri

et al. 2022

Preprint

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Energy storage is a vital aspect for the successful implementation of renewable energy resources on a global scale. Herein, we investigated the redox cycle of nickel (II) bis(diethyldithiocarbamate), NiII(dtc)2, for potential use as a multi-electron storage catholyte in non-aqueous redox flow batteries (RFBs). Previous studies have shown the unique redox cycle of NiII(dtc)2 offers 2e- chemistry upon oxidation from NiII → NiIV but 1e- chemistry upon reduction from NiIV → NiIII → NiII. Electrochemical experiments presented here show that the addition of as little as 10 mol% ZnII(ClO4)2 to the electrolyte consolidates the two 1e- reduction peaks into a single 2e- reduction where [NiIV(dtc)3]+ is reduced directly to NiII(dtc)2. This catalytic enhancement is believed to be due to ZnII removal of a dtc- ligand from a NiIII(dtc)3 intermediate, resulting in more facile reduction to NiII(dtc)2. The addition of ZnII also improves the 2e- oxidation, shifting the anodic peak negative and decreasing the 2e- peak splitting. H-cell cycling experiments showed that 97% coulombic efficiency and 98% charge storage efficiency was maintained for 50 cycles over 25 h using 0.1 M ZnII(ClO4)2 as supporting electrolyte. If ZnII(ClO4)2 was replaced with TBAPF6 in the electrolyte, the coulombic efficiency fell to 78%. The use of ZnII to increase the reversibility of 2e- transfer is a promising result that points to the ability to use nickel dithiocarbonates for multi-electron storage in RFBs.

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Controlling One-Electron vs Two-Electron Pathways in the Multi-Electron Redox Cycle of Nickel Diethyldithiocarbamate

Cited by 3 publications

References 19 publications

Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi-Electron Storage in Redox Flow Batteries

Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi-Electron Storage in Redox Flow Batteries

Temperature-dependent study of AcFc-FeIII(acac)3 redox couple for non-aqueous redox flow battery

A Zinc Catalyzed Two-Electron Nickel(IV/II) Redox Couple: New Catholyte Design for Redox Flow Batteries

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