Mechanisms of Reaction Between Co(II) Complexes and Peroxymonosulfate

Dror Shamir; Dan Meyerstein; Dmitry Katsaran; Lyudmila Pochtarenko; Guy Yardeni; Ariela Burg; Yael Albo; Haya Kornweitz; Israel Zilbermann

doi:10.1002/ejic.202100646

Mechanisms of Reaction Between Co(II) Complexes and Peroxymonosulfate

Dror Shamir, Dan Meyerstein, Dmitry Katsaran, Lyudmila Pochtarenko, Guy Yardeni, Ariela Burg, Yael Albo, Haya Kornweitz, Israel Zilbermann

Ben-Gurion University of the Negev, Ariel University

Research output: Contribution to journal › Article › peer-review

Abstract

Advanced oxidation technologies often use peroxymonosulfate in the presence of Co^II_aq. It is commonly assumed that the reaction of Co(H₂O)₆²⁺ with HSO₅⁻ yields Co^III_aq and SO₄^.−. DFT results point out that first Co^II(SO₅)(H₂O)₂ is formed. The homolysis of Co^II(SO₅)(H₂O)₂ to yield (H₂O)Co^II(SO₅)OH^.+SO_4.⁻, is exothermic but has a large activation energy. However the cobalt is not oxidized in this reaction. Co^II(SO₅)(H₂O)₂ reacts with a second HSO₅⁻ to form Co^II(SO₅)₂(H₂O)²⁻ that decomposes via disproportionation of the monoperoxysulfate ions without oxidation of the central cobalt ion. Surprisingly even in the presence of ligands, L, that stabilize Co^III, i. e., pyrophosphate; tri-polyphosphate and ATP, the experimentally observed reaction mechanism involves the formation of LCo^II-OOSO_3aq which then reacts with another HSO₅⁻ to form LCo^II-(OOSO₃²⁻)₂. The latter complex decomposes via disproportionation of the monoperoxysulfate ligands followed by oxidation of the central cobalt cation. Alternatively, in the presence of excess Co^IIL_aq, LCo^II-OOSO_3aq reacts with Co^IIL_aq to form 2Co^IIIL_aq. These results point out that the mechanism of advanced oxidation processes initiated by a mixture of Co(H₂O)₆²⁺ and HSO₅⁻ must be re-considered.

Original language	English
Article number	e202100646
Pages (from-to)	e202100646
Journal	European Journal of Inorganic Chemistry
Volume	2022
Issue number	1
DOIs	https://doi.org/10.1002/ejic.202100646
State	Published - 11 Jan 2022

Keywords

Catalytic processes
Cobalt(II)
Fenton like mechanism
Oxidation Processes
Peroxymonosulfate

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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10.1002/ejic.202100646

https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejic.202100646

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title = "Mechanisms of Reaction Between Co(II) Complexes and Peroxymonosulfate",

abstract = "Advanced oxidation technologies often use peroxymonosulfate in the presence of CoIIaq. It is commonly assumed that the reaction of Co(H2O)62+ with HSO5− yields CoIIIaq and SO4.−. DFT results point out that first CoII(SO5)(H2O)2 is formed. The homolysis of CoII(SO5)(H2O)2 to yield (H2O)CoII(SO5)OH.+SO4.−, is exothermic but has a large activation energy. However the cobalt is not oxidized in this reaction. CoII(SO5)(H2O)2 reacts with a second HSO5− to form CoII(SO5)2(H2O)2− that decomposes via disproportionation of the monoperoxysulfate ions without oxidation of the central cobalt ion. Surprisingly even in the presence of ligands, L, that stabilize CoIII, i. e., pyrophosphate; tri-polyphosphate and ATP, the experimentally observed reaction mechanism involves the formation of LCoII-OOSO3aq which then reacts with another HSO5− to form LCoII-(OOSO32−)2. The latter complex decomposes via disproportionation of the monoperoxysulfate ligands followed by oxidation of the central cobalt cation. Alternatively, in the presence of excess CoIILaq, LCoII-OOSO3aq reacts with CoIILaq to form 2CoIIILaq. These results point out that the mechanism of advanced oxidation processes initiated by a mixture of Co(H2O)62+ and HSO5− must be re-considered.",

keywords = "Catalytic processes, Cobalt(II), Fenton like mechanism, Oxidation Processes, Peroxymonosulfate",

author = "Dror Shamir and Dan Meyerstein and Dmitry Katsaran and Lyudmila Pochtarenko and Guy Yardeni and Ariela Burg and Yael Albo and Haya Kornweitz and Israel Zilbermann",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2022",

month = jan,

day = "11",

doi = "10.1002/ejic.202100646",

language = "الإنجليزيّة",

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pages = "e202100646",

journal = "European Journal of Inorganic Chemistry",

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TY - JOUR

T1 - Mechanisms of Reaction Between Co(II) Complexes and Peroxymonosulfate

AU - Shamir, Dror

AU - Meyerstein, Dan

AU - Katsaran, Dmitry

AU - Pochtarenko, Lyudmila

AU - Yardeni, Guy

AU - Burg, Ariela

AU - Albo, Yael

AU - Kornweitz, Haya

AU - Zilbermann, Israel

PY - 2022/1/11

Y1 - 2022/1/11

N2 - Advanced oxidation technologies often use peroxymonosulfate in the presence of CoIIaq. It is commonly assumed that the reaction of Co(H2O)62+ with HSO5− yields CoIIIaq and SO4.−. DFT results point out that first CoII(SO5)(H2O)2 is formed. The homolysis of CoII(SO5)(H2O)2 to yield (H2O)CoII(SO5)OH.+SO4.−, is exothermic but has a large activation energy. However the cobalt is not oxidized in this reaction. CoII(SO5)(H2O)2 reacts with a second HSO5− to form CoII(SO5)2(H2O)2− that decomposes via disproportionation of the monoperoxysulfate ions without oxidation of the central cobalt ion. Surprisingly even in the presence of ligands, L, that stabilize CoIII, i. e., pyrophosphate; tri-polyphosphate and ATP, the experimentally observed reaction mechanism involves the formation of LCoII-OOSO3aq which then reacts with another HSO5− to form LCoII-(OOSO32−)2. The latter complex decomposes via disproportionation of the monoperoxysulfate ligands followed by oxidation of the central cobalt cation. Alternatively, in the presence of excess CoIILaq, LCoII-OOSO3aq reacts with CoIILaq to form 2CoIIILaq. These results point out that the mechanism of advanced oxidation processes initiated by a mixture of Co(H2O)62+ and HSO5− must be re-considered.

AB - Advanced oxidation technologies often use peroxymonosulfate in the presence of CoIIaq. It is commonly assumed that the reaction of Co(H2O)62+ with HSO5− yields CoIIIaq and SO4.−. DFT results point out that first CoII(SO5)(H2O)2 is formed. The homolysis of CoII(SO5)(H2O)2 to yield (H2O)CoII(SO5)OH.+SO4.−, is exothermic but has a large activation energy. However the cobalt is not oxidized in this reaction. CoII(SO5)(H2O)2 reacts with a second HSO5− to form CoII(SO5)2(H2O)2− that decomposes via disproportionation of the monoperoxysulfate ions without oxidation of the central cobalt ion. Surprisingly even in the presence of ligands, L, that stabilize CoIII, i. e., pyrophosphate; tri-polyphosphate and ATP, the experimentally observed reaction mechanism involves the formation of LCoII-OOSO3aq which then reacts with another HSO5− to form LCoII-(OOSO32−)2. The latter complex decomposes via disproportionation of the monoperoxysulfate ligands followed by oxidation of the central cobalt cation. Alternatively, in the presence of excess CoIILaq, LCoII-OOSO3aq reacts with CoIILaq to form 2CoIIILaq. These results point out that the mechanism of advanced oxidation processes initiated by a mixture of Co(H2O)62+ and HSO5− must be re-considered.

KW - Catalytic processes

KW - Cobalt(II)

KW - Fenton like mechanism

KW - Oxidation Processes

KW - Peroxymonosulfate

UR - http://www.scopus.com/inward/record.url?scp=85121364739&partnerID=8YFLogxK

U2 - 10.1002/ejic.202100646

DO - 10.1002/ejic.202100646

M3 - مقالة

SN - 1434-1948

VL - 2022

SP - e202100646

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 1

M1 - e202100646

ER -

Mechanisms of Reaction Between Co(II) Complexes and Peroxymonosulfate

Abstract

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