Dissociative electron transfer mechanism and application in the electrocatalytic activation of organic halides
Source abstract
Abstract
The electrochemical dehalogenation of organic halides has been a widely investigated topic in primis for fundamental investigations of dissociative electron transfer (DET) and as a green way for the electrosynthesis of organic compounds and environmental remediation. The main drawback associated with the electrochemical activation of C-X is the very negative potentials required, and this is particularly true in the case of organic chlorides, which represent the most investigated ensemble among organic molecules containing a leaving group. This has boosted over the last decades the research of electrode materials that are active toward C-X bond breaking, and without any doubt, Ag possesses extraordinary electrocatalytic properties, so far unsurpassed by any other electrode material. In this paper, we will attempt to brush up on important concepts related to DET in organic halides, while also evaluating recent developments in terms of electrode materials used in electrosynthesis based on organic halides and R-X degradation processes.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: CO2 Reduction Techniques and Catalysts · Radical Photochemical Reactions · Electrochemical Analysis and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (69)
Show source-provided references
1. Electrochemical hydrodehalogenation of polychloromethanes at silver and carbon electrodes10.1016/j.apcatb.2008.10.010 ↗
2. Electrocatalytic dechlorination of polychloroethylenes at silver cathode10.1007/s10800-012-0483-4 ↗
3. Successive removal of chloride ions from organic polychloride pollutants. Mechanisms of reductive electrochemical elimination in aliphatic gem-polychlorides, α,β-polychloroalkenes, and α,β-polychloroalkanes in mildly protic medium10.1021/ja036141t ↗
4. Off J Eur Union · 2019 · L315
5. Toward resolving the budget discrepancy of ozone-depleting carbon tetrachloride (CCl& lt;sub& gt;4& lt;/sub& gt;): an analysis of top-down emissions from China10.5194/acp-18-11729-2018 ↗
6. Hydrodehalogenation of polychloromethanes on silver-based gas diffusion electrodes10.1002/celc.202100379 ↗
7. One-pot synthesis of benzoic acid by electrocatalytic reduction of bromobenzene in the presence of CO210.1016/j.elecom.2011.05.009 ↗
8. Toward green syntheses of carboxylates: considerations of mechanisms and reactions at the electrodes for electrocarboxylation of organohalides and alkenes10.1016/S1872-2067(22)64180-9 ↗
9. Electron transfer and bond breaking: recent advances10.1016/j.chemphys.2005.09.029 ↗
10. Fragmentation of aryl halide π anion radicals. Bending of the cleaving bond and activation vs driving force relationships10.1021/ja045989u ↗
11. Dissociative electron transfer to haloacetonitriles. An example of the dependency of in-cage ion-radical interactions upon the leaving group10.1021/ja0275212 ↗
12. Activation of the carbon– halogen bond
13. Passage from stepwise to concerted dissociative electron transfer through modulation of electronic states coupling10.1002/chem.200801240 ↗
14. Can single-electron transfer break an aromatic carbon - heteroatom bond in one step? A novel example of transition between stepwise and concerted mechanisms in the reduction of aromatic iodides10.1021/ja991365q ↗
15. Silver nanoparticles deposited on glassy carbon. Electrocatalytic activity for reduction of benzyl chloride10.1016/j.elecom.2006.08.001 ↗
16. Electrochemical reduction of benzyl halides at a silver electrode10.1016/j.electacta.2006.01.039 ↗
17. A DFT and SERS study of synergistic roles of thermodynamics and kinetics during the electrocatalytic reduction of benzyl chloride at silver cathodes
18. Integrating single-cobalt-site and electric field of boron nitride in dechlorination electrocatalysts by bioinspired design10.1038/s41467-020-20619-w ↗
19. Electrochemical synthesis of adiponitrile from the renewable raw material glutamic acid10.1002/cssc.201100776 ↗
20. Electrochemical reduction of halogenated aromatic compounds at metal cathodes in acetonitrile10.1016/j.electacta.2019.135484 ↗
21. Dissociative electron transfer to organic chlorides: electrocatalysis at metal cathodes10.1039/b719936h ↗
22. Influence of halide ions on the electrochemical reduction of carbon dioxide over a copper surface10.1039/D1TA09125E ↗
23. The one-electron cleavage and reductive homo-coupling of alkyl bromides at silver–palladium cathodes10.1016/j.jelechem.2008.07.021 ↗
24. The copper–palladium cathode to achieve pure one-electron cleavages: the case of alkyl bromides10.1016/j.elecom.2005.04.010 ↗
25. Electrocatalysis on silver and silver alloys for dichloromethane and trichloromethane dehalogenation10.1016/j.electacta.2003.12.061 ↗
26. Electrocatalytic properties of transition metals toward reductive dechlorination of polychloroethanes10.1016/j.electacta.2012.03.009 ↗
27. In situ identification of intermediates of benzyl chloride reduction at a silver electrode by SERS coupled with DFT calculations10.1021/ja1024639 ↗
28. Electrochemical reduction of halogenated alkanes and alkenes using activated carbon-based cathodes10.1021/acs.est.2c05608 ↗
29. Silver nanoparticles deposited on glassy carbon. Electrocatalytic activity for reduction of benzyl chloride10.1016/j.elecom.2006.08.001 ↗
30. Electrochemical activation of carbon–halogen bonds: electrocatalysis at silver/copper nanoparticles10.1016/j.apcatb.2014.04.023 ↗
31. A facile approach to silver nanowire array electrode preparation and its application for chloroform reduction10.1016/j.electacta.2020.137110 ↗
32. Mechanistic insight into the electrocatalytic performance of reduced graphene oxide supported palladium, silver and palladium-silver nanodeposits toward electro-dehalogenation of halocarbons in room temperature ionic liquids10.1039/D0CP01932A ↗
33. Ultrafine palladium nanoparticles supported on 3D self-supported Ni foam for cathodic dechlorination of florfenicol10.1016/j.cej.2018.11.099 ↗
34. Organohalide respiring bacteria and reductive dehalogenases: key tools in organohalide bioremediation10.3389/fmicb.2016.00249 ↗
35. Reductive dehalogenase structure suggests a mechanism for B12-dependent dehalogenation10.1038/nature13901 ↗
36. Efficient Co-MoS2 electrocatalyst for cathodic degradation of halogenated disinfection by-products in water sample10.1016/j.seppur.2020.118085 ↗
37. Corbin · 2022
38. Contributions of organic electrosynthesis to green chemistry
39. Electrocatalytic activation of organic chlorides via direct and indirect electron transfer using atomic vacancy control of palladium-based catalyst10.1016/j.xcrp.2021.100713 ↗
40. Recent advances in electrocatalysts for halogenated organic pollutant degradation10.1039/C9EN00411D ↗
41. Electroreduction of acetochlor at silver cathodes in aqueous media10.1149/1945-7111/ac13d6 ↗
42. Electrocatalytic carboxylation of benzyl chlorides at silver cathodes in acetonitrile10.1039/b206746c ↗
43. Mechanism of the electrochemical reduction of benzyl chlorides catalysed by Co(salen)10.1016/S0022-0728(97)00572-X ↗
44. Nickel(I)(salen)-electrocatalyzed reduction of benzyl chlorides in the presence of carbon dioxide10.1016/S0022-0728(01)00373-4 ↗
45. Electrochemical synthesis of cyanoacetic acid from chloroacetonitrile and carbon dioxide10.1149/1.1490358 ↗
46. Electrocatalytic activation of aromatic carbon-bromine bonds toward carboxylation at silver and copper cathodes10.1149/2.008307jes ↗
47. Electrocatalytic carboxylation of chloroacetonitrile at a silver cathode for the synthesis of cyanoacetic acid10.1016/j.electacta.2008.07.012 ↗
48. Relative activity of metal cathodes towards electroorganic coupling of CO2 with benzylic halides10.1016/j.electacta.2021.138528 ↗
49. Electrocatalytic carboxylation of halogenated compounds with mesoporous silver electrode materials10.1039/D1RA02563E ↗
50. Highly efficient electrocatalytic carboxylation of 1-phenylethyl chloride at Cu foam cathode10.3390/catal8070273 ↗
51. Electrochemical CO2 fixation to α-methylbenzyl bromide in divided cells with nonsacrificial anodes and aqueous anolytes10.1021/acssuschemeng.9b04647 ↗
52. Electrocarboxylation of halobenzonitriles: an environmentally friendly synthesis of phthalate derivatives10.1016/j.electacta.2019.134576 ↗
53. Electrocarboxylation of 1-chloro-(4-isobutylphenyl)ethane with a silver cathode in ionic liquids: an environmentally benign and efficient way to synthesize Ibuprofen10.1039/C9RA01781J ↗
54. Electrocatalytic processes for the valorization of CO2: synthesis of cyanobenzoic acid using eco-friendly strategies10.3390/catal9050413 ↗
55. Facile and economical electrochemical dehalogenative deuteration of (hetero)aryl halides10.31635/ccschem.020.202000512 ↗
56. Insights into electroreductive dehalogenation mechanisms of chlorinated environmental pollutants10.1002/celc.202000067 ↗
57. Electroreduction of volatile organic halides on activated silver cathodes10.1007/s10800-005-0798-5 ↗
58. Electrocatalytic dechlorination of volatile organic compounds at a copper cathode. Part I: polychloromethanes10.1016/j.apcatb.2012.07.004 ↗
59. Electrocatalytic dechlorination of volatile organic compounds at copper cathode. Part II: polychloroethanes10.1016/j.apcatb.2012.07.003 ↗
60. Electroreduction of volatile organic halides on activated silver cathodes10.1007/s10800-005-0798-5 ↗
61. Direct electrochemical reduction of acetochlor at carbon and silver cathodes in dimethylformamide10.1149/1945-7111/abb8f9 ↗
62. Electrocatalytic dechlorination of 2,4-DCBA using CTAB functionalized Pd/GAC movable granular catalyst: role of adsorption in catalysis10.1016/j.cej.2021.128758 ↗
63. MOF-derived single site catalysts with Electron-Rich Fe-N4 sites for efficient elimination of trichloroacetamide DBP10.1016/j.cej.2022.137060 ↗
64. Active sites in single-atom Fe–nx–C nanosheets for selective electrochemical dechlorination of 1,2-dichloroethane to ethylene10.1021/acsnano.0c02783 ↗
65. Efficient carboxylation of styrene and carbon dioxide by single-atomic copper electrocatalyst10.1016/j.jcis.2021.05.105 ↗
66. Pyridinic nitrogen enables dechlorination of trichloroethylene to acetylene by green rust: performance, mechanism and applications10.1016/j.scitotenv.2022.153825 ↗
67. Effects of oxygen functional groups on electrochemical performance of carbon materials for dechlorination of 1,2-dichloroethane to ethylene10.1016/j.cej.2022.134547 ↗
68. Identification of catalytic active sites in nitrogen-doped carbon for electrocatalytic dechlorination of 1,2-dichloroethane10.1021/acscatal.9b02853 ↗
69. Electrocatalysis at palladium nanoparticles: effect of the support nitrogen doping on the catalytic activation of carbon-halogen bond10.1016/j.apcatb.2013.07.023 ↗