Dataset Information

Membrane-Modified Metal Triazole Complexes for the Electrocatalytic Reduction of Oxygen and Carbon Dioxide.

ABSTRACT: In this manuscript, an electrochemical architecture is designed that controls the kinetics of proton transfer to metal triazole complexes for electrocatalytic O₂ and CO₂ reduction. Self-assembled monolayers of these catalysts are attached to a glassy carbon electrode and covered with a lipid monolayer containing proton carriers, which acts as a proton-permeable membrane. The O₂ reduction voltammograms on carbon are similar to those obtained on membrane-modified Au electrodes, which through the control of proton transfer rates, can be used to improve the selectivity of O₂ reduction. The improved voltage stability of the carbon platforms allows for the investigation of a CO₂ reduction catalyst inside a membrane. By controlling proton transfer kinetics across the lipid membrane, it is found that the relative rates of H₂, CO, and HCOOH production can be modulated. It is envisioned that the use of these membrane-modified carbon electrodes will aid in understanding catalytic reactions involving the transfer of multiple protons and electrons.

SUBMITTER: Supakul SN

PROVIDER: S-EPMC6232292 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Membrane-Modified Metal Triazole Complexes for the Electrocatalytic Reduction of Oxygen and Carbon Dioxide.

Supakul Skye N SN Barile Christopher J CJ

Frontiers in chemistry 20181106

In this manuscript, an electrochemical architecture is designed that controls the kinetics of proton transfer to metal triazole complexes for electrocatalytic O2 and CO2 reduction. Self-assembled monolayers of these catalysts are attached to a glassy carbon electrode and covered with a lipid monolayer containing proton carriers, which acts as a proton-permeable membrane. The O2 reduction voltammograms on carbon are similar to those obtained on membrane-modified A ...[more]

PMID: 30460230

Similar Datasets

Project description:The synthesis of coinage metal aluminyl complexes, featuring M-Al covalent bonds, is reported via a salt metathesis approach employing an anionic Al(i) ('aluminyl') nucleophile and group 11 electrophiles. This approach allows access to both bimetallic (1 : 1) systems of the type ( t Bu3P)MAl(NON) (M = Cu, Ag, Au; NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) and a 2 : 1 di(aluminyl)cuprate system, K[Cu{Al(NON)}2]. The bimetallic complexes readily insert heteroallenes (CO2, carbodiimides) into the unsupported M-Al bonds to give systems containing a M(CE2)Al bridging unit (E = O, NR), with the μ-κ1(C):κ2(E,E') mode of heteroallene binding being demonstrated crystallographically for carbodiimide insertion in the cases of all three metals, Cu, Ag and Au. The regiochemistry of these processes, leading to the formation of M-C bonds, is rationalized computationally, and is consistent with addition of CO2 across the M-Al covalent bond with the group 11 metal acting as the nucleophilic partner and Al as the electrophile. While the products of carbodiimide insertion are stable to further reaction, their CO2 analogues have the potential to react further, depending on the identity of the group 11 metal. ( t Bu3P)Au(CO)2Al(NON) is inert to further reaction, but its silver counterpart reacts slowly with CO2 to give the corresponding carbonate complex (and CO), and the copper system proceeds rapidly to the carbonate even at low temperatures. Experimental and quantum chemical investigations of the mechanism of the CO2 to CO/carbonate transformation are consistent with rate-determining extrusion of CO from the initially-formed M(CO)2Al fragment to give a bimetallic oxide that rapidly assimilates a second molecule of CO2. The calculated energetic barriers for the most feasible CO extrusion step (ΔG ‡ = 26.6, 33.1, 44.5 kcal mol-1 for M = Cu, Ag and Au, respectively) are consistent not only with the observed experimental labilities of the respective M(CO)2Al motifs, but also with the opposing trends in M-C (increasing) and M-O bond strengths (decreasing) on transitioning from Cu to Au.

Dataset Information

Membrane-Modified Metal Triazole Complexes for the Electrocatalytic Reduction of Oxygen and Carbon Dioxide.

Publications

Membrane-Modified Metal Triazole Complexes for the Electrocatalytic Reduction of Oxygen and Carbon Dioxide.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets