Building up an electrocatalytic activity scale of cathode materials for organic halide reductions

Bellomunno, C.; Bonanomi, D.; Falciola, L.; Longhi, Mariangela; Mussini, Patrizia R.; Doubova, L.; Silvestro, Giuseppe Di

doi:10.1016/j.electacta.2004.10.047

Cited by 72 publications

(50 citation statements)

References 27 publications

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“…Such electrocatalytic conditions allow working at remarkably milder potentials, and in many cases improve the selectivity of the reaction and/or significantly affect the nature of the reduction products. Pd [4][5][6][7][8][9][10][11], Cu [10][11][12] and, above all, Ag [3,[13][14][15][16][17][18][19] have high and reproducible catalytic activities for the electrochemical reduction of organic halides, whereas milder and/ or less reproducible activities are exhibited by other metals including Hg, Pb and Au [13,14]. Actually, according to theoretical studies, Au has the highest intrinsic affinity for halide anions [20,21], which is confirmed by experimental determination of the amount of halide anions specifically adsorbed on different metals in water at the potential of zero charge (PZC), showing the following order of increasing affinity [22,23]:…”

Section: Introductionmentioning

confidence: 99%

The solvent effect on the electrocatalytic cleavage of carbon-halogen bonds on Ag and Au

Arnaboldi

Gennaro

Isse

et al. 2015

Electrochimica Acta

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In recent years it has been shown in detail how the electrocatalytic cleavage of carbon-halogen bonds is\ud modulated by (a) the stepwise or concerted nature of the dissociative electron-transfer mechanism,\ud which is inﬂ uenced by the nature of the electrode surface, the type of halogen atom and the molecular\ud structure of RX as a whole, and (b) the double-layer structure (as a function of the nature and bulkiness of\ud the supporting electrolyte ions). In order to both complete and support the interpretative scheme thus\ud developed, this work is focused on the solvent role. When one compares aprotic with protic organic\ud solvents af ter appropriate intersolvental normalization, interesting peculiarities emerge, especially\ud concerning protic media. Solvent proticity deeply affects both the reaction mechanism (on both noncatalytic\ud and catalytic electrodes) and the extent of the catalytic effects. These items are discussed on the\ud basis of a complete investigation carried out with a carefully controlled experimental protocol on two\ud chloride and bromide couples, one aromatic and one aliphatic, representative of stepwise and concerted\ud mechanisms, respectively, in four aprotic and four protic solvents, on both non catalytic GC and catalytic\ud Ag and Au electrodes. The results are discussed in the framework of a recently developed interpretative\ud scheme of the carbon-halogen cleavage mechanism

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Section: Introductionmentioning

confidence: 99%

The solvent effect on the electrocatalytic cleavage of carbon-halogen bonds on Ag and Au

Arnaboldi

Gennaro

Isse

et al. 2015

Electrochimica Acta

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“…Thus, in the case of cathodic materials possessing catalytic activities such as Ag [13][14][15][16][19][20][21][22], Cu [21,23,24] and Pd [21,25,26], there are significant interactions between the electrode surface and, possibly the reagents, products, and mainly the activated complex [21], resulting in a lowering of the activation energy of the ET. As a consequence, the reduction process occurs at more positive potentials (less overpotential is required) with respect to a non-catalytic electrode.…”

Section: Aliphatic Halidesmentioning

confidence: 99%

“…We have been active in the field of electrocatalytic activation of organic halides for several years. In particular, we focused our attention on silver [9][10][11][12][13][14], which is among the best catalytic materials for the reduction of RX [15].…”

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confidence: 99%

Electrocatalysis and electron transfer mechanisms in the reduction of organic halides at Ag

et al. 2009

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The reductive cleavage of a series of organic halides, including both aromatic and aliphatic compounds, has been investigated in acetonitrile at glassy carbon and silver electrodes. Ag exhibits extraordinary electrocatalytic activities for the reduction of most of the investigated halides. During the reductive cleavage of a carbon-halogen bond, electron transfer (ET) and bond breaking may occur either in a single step or in two distinct steps. The compounds examined in this study are representative of both dissociative electron transfer (DET) mechanisms. In general a link between the DET mechanism and electrocatalysis at Ag is observed for the whole set of data. There is no catalysis at all when the ET involves a substituent that gives a stable radical anion. Furthermore, there is no catalysis for all aromatic chlorides. Instead, a remarkable electrocatalysis is observed for all compounds undergoing a concerted DET mechanism, regardless of the nature of the halogen atom.

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“…As shown in curves b and e, the two reduction peaks shifted to a more positive potential because of the electrocatalytic properties of the Ag electrode. The electrocatalytic activities of electrode materials for the reduction of organic halides have been the subject of many studies [18,19,21,22,[52][53][54]. These studies have shown that Ag exhibits powerful electrocatalytic activities toward the reduction of various organic halides.…”

Section: Introductionmentioning

confidence: 99%

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

et al. 2017

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Carbon dioxide (CO 2 ) is the largest contributor to the greenhouse effect, and fixing and using this greenhouse gas in a facile manner is crucial. This work investigates the electrocarboxylation of dichlorobenzenes with the atmospheric pressure of CO 2 in an undivided cell with an Ag cathode and an Mg sacrificial anode. The corresponding carboxylic acids and their derivatives, which are important industrial and fine chemicals, are obtained. To deeply understand this reaction, we investigate the influence of various reaction conditions, such as supporting electrolyte, current density, electric charge, and reaction temperature, on the electrocarboxylation yield by using 1,4-dichlorobenzene as the model compound. The electrochemical behavior of dichlorobenzenes is studied through cyclic voltammetry. The relation among the distinct electronic effects of dichlorobenzenes, the electrochemical characteristics of their reduction, and the distribution law of target products is also established.

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Building up an electrocatalytic activity scale of cathode materials for organic halide reductions

Cited by 72 publications

References 27 publications

The solvent effect on the electrocatalytic cleavage of carbon-halogen bonds on Ag and Au

The solvent effect on the electrocatalytic cleavage of carbon-halogen bonds on Ag and Au

Electrocatalysis and electron transfer mechanisms in the reduction of organic halides at Ag

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

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