Homogeneous and heterogeneous electrocatalytic reduction of halo-organic compounds by (NiIILi)2+ (Li= tetraaza-macrocyclic ligand) in aqueous solutions

Albo, Yael; Shandalov, Elisabetha; Hayoun, Lior; Zilbermann, Israel; Maimon, Eric; Meyerstein, Dan

doi:10.1016/j.ica.2017.06.066

Cited by 7 publications

(2 citation statements)

References 59 publications

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“…Many coordination complexes catalyzing the electrochemical reduction of halogenated compounds have been proposed in literature, although their catalytic activity towards the reduction of halogen bonds in aqueous medium has not always been demonstrated [12-15]. Among them, Ni(I)(cyclam) derivatives have shown a good catalytic activity towards the reduction of bromoacetic and benzoic acids, propargyloxy and allyloxy -bromoester, epichlorohydrin and 1,3-dichloropropane in hydroalcoholic and aqueous media [16][17][18][19][20].…”

Section: Indirect Electrolysismentioning

confidence: 99%

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

Geneste

2018

Current Opinion in Electrochemistry

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Highlights  Improvement of biodegradability by catalytic electrochemical processes  Coupling a catalytic electrochemical pre-treatment with a biological process for remediation  Targeting specific functional groups to improve the biodegradability of persistent compounds  Indirect electrolysis and electrocatalysis as selective and well-controlled pretreatments ACCEPTED MANUSCRIPTElectrochemical advanced oxidation processes have been widely explored for the total degradation of biorecalcitrant compounds such as some pesticides and pharmaceuticals. More recently, coupling processes involving an electrochemical pre-treatment followed by a biological process have been proposed as cost-effective and reliable remediation methods for the mineralization of persistent compounds. This open the way to more selective electrochemical methods than those involving hydroxyl radicals since the aim of the pretreatment is no more to achieve the total mineralization of non-biodegradable species, but is only the improvement of their biodegradability focusing on functional groups known to reduce it. In this context, catalytic electrochemical reductions and oxidations can find their place in a coupling process for the remediation of biorecalcitrant compounds as selective and well-controlled methods. This review summarizes some relevant and recent work on catalytic electrochemical processes performed in aqueous medium that have been used to improve the biodegradability of persistent organic pollutants.

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Section: Indirect Electrolysismentioning

confidence: 99%

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

Geneste

2018

Current Opinion in Electrochemistry

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“…In contrast, molecular catalysts are attractive due to (1) facile property tuning from ligand modification, (2) easy selectivity and activity evaluation by incorporation of various types of metal to the catalysts, and (3) low metal content used. The catalysts for these systems typically contain ligands, such as salen, , alamin, − tetrapyrrole, − and polypyridyl family, , that are utilized in coordination complexes with metal centers such as cobalt, iron, and nickel. ,− Salen-containing metal complexes such as nickel(I) salen and cobalt(I) salen ( MSalen in Chart ) have been reported to facilitate the electron transfer reaction during dehalogenation. , The nickel(II) tetraazamacrocyclic complex ( NiTAM in Chart ) also presented dehalogenative activity toward various bromo- and iodo- compounds . Dobson and Saini developed a Co(II)-porphyrin complex ( CoPor in Chart ) for the detection and quantification of a series of organohalides via an electrocatalytic dehalogenation mechanism. ,, Although most molecular catalytic systems are homogeneous, molecular catalysts can also be heterogenized to reduce the amount of catalyst needed compared to a homogeneous system, which also facilitate catalyst recycling.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Dechlorination of Dichloromethane in Water Using a Heterogenized Molecular Copper Complex

et al. 2021

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The remediation of organohalides from water is a challenging process in environment protection and water treatment. Herein, we report a molecular copper(I) complex with two triazole units, CuT2, in a heterogeneous aqueous system that is capable of dechlorinating dichloromethane (CH 2 Cl 2 ) to afford hydrocarbons (methane, ethane, and ethylene). The catalytic performance is evaluated in water and presented high Faradaic efficiency (average 70% CH 4 ) across a range of potentials (−1.1 to −1.6 V vs Ag/AgCl) and high activity (maximum −25.1 mA/cm 2 at −1.6 V vs Ag/AgCl) with a turnover number of 2.0 × 10 7 . The CuT2 catalyst also showed excellent stability for 14 h of constant exposure to CH 2 Cl 2 and 10 h of CH 2 Cl 2 exposure cycling. The control compound, a copper-free triazole unit (T1), was also investigated under the same condition and showed inferior catalytic activity, indicating the importance of the copper center. Plausible catalytic mechanisms are proposed for the formation of C 1 and C 2 products via radical intermediates. Computational studies provided additional insight into the reaction mechanism and the selectivity toward the CH 4 formation. The findings in this study demonstrate that complex CuT2 is an efficient and stable catalyst for the dehalogenation of CH 2 Cl 2 and could potentially be used for the exploration of the removal of halogenated species from aqueous systems.

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Stabilization of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)⁺ in a Sol‐Gel Matrix: It's Plausible Use in Catalytic Processes

Shamir¹,

Wolfer

Shames

et al. 2020

Israel Journal of Chemistry

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Monovalent nickel is used as a catalyst in a diversity of important chemical systems due to its properties as a strong reducing agent. However, monovalent nickel is unstable in homogeneous systems; its lifetime is very short, and therefore, its efficiency as a catalyst is quite limited. In this article, we demonstrate the catalytic capabilities of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)+ as a reducing and catalytic agent by its entrapment in the silica sol gel matrix. The EPR results indicate that the sol‐gel matrix plays two roles: it inhibits the common mechanism of Ni(I)L+ decomposition in aqueous solutions, and it also facilitates its functionality as a heterogeneous catalyst, by stabilizing it for at least several hours. The activity of Ni(I)L+ which is entrapped within the matrix, was studied by reducing 2,2‐Bis(bromomethyl)‐1,3‐Propanediol and I3−. The results indicate that Ni(I)L+/Ni(III)L−H2+ acts as a good reducing agent. These results have important implications for a variety of essential catalytic reactions by shedding light on a new feature of sol‐gel matrices and their use as active species stabilizers.

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Homogeneous and heterogeneous electrocatalytic reduction of halo-organic compounds by (NiIILi)2+ (Li= tetraaza-macrocyclic ligand) in aqueous solutions

Cited by 7 publications

References 59 publications

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

Electrocatalytic Dechlorination of Dichloromethane in Water Using a Heterogenized Molecular Copper Complex

Stabilization of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)⁺ in a Sol‐Gel Matrix: It's Plausible Use in Catalytic Processes

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Homogeneous and heterogeneous electrocatalytic reduction of halo-organic compounds by (NiIILi)2+ (Li= tetraaza-macrocyclic ligand) in aqueous solutions

Cited by 7 publications

References 59 publications

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

Electrocatalytic Dechlorination of Dichloromethane in Water Using a Heterogenized Molecular Copper Complex

Stabilization of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)+ in a Sol‐Gel Matrix: It's Plausible Use in Catalytic Processes

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Stabilization of Ni(I)(1,4,8,11‐tetraazacyclotetradecane)⁺ in a Sol‐Gel Matrix: It's Plausible Use in Catalytic Processes