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Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate.

ABSTRACT: Electrocatalytic methods for organic synthesis could offer sustainable alternatives to traditional redox reactions, but strategies are needed to enhance the performance of molecular catalysts designed for this purpose. The synthesis of a pyrene-tethered TEMPO derivative (TEMPO=2,2,6,6-tetramethylpiperidinyl-N-oxyl) is described, which undergoes facile in?situ noncovalent immobilization onto a carbon cloth electrode. Cyclic voltammetry and controlled potential electrolysis studies demonstrate that the immobilized catalyst exhibits much higher activity relative to 4-acetamido-TEMPO, an electronically similar homogeneous catalyst. In preparative electrolysis experiments with a series of alcohol substrates and the immobilized catalyst, turnover numbers and frequencies approach 2?000 and 4?000?h-1 , respectively. The synthetic utility of the method is further demonstrated in the oxidation of a sterically hindered hydroxymethylpyrimidine precursor to the blockbuster drug, rosuvastatin.

SUBMITTER: Das A

PROVIDER: S-EPMC5831151 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature

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Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate.

Das Amit A Stahl Shannon S SS

Angewandte Chemie (International ed. in English) 20170621 30

Electrocatalytic methods for organic synthesis could offer sustainable alternatives to traditional redox reactions, but strategies are needed to enhance the performance of molecular catalysts designed for this purpose. The synthesis of a pyrene-tethered TEMPO derivative (TEMPO=2,2,6,6-tetramethylpiperidinyl-N-oxyl) is described, which undergoes facile in situ noncovalent immobilization onto a carbon cloth electrode. Cyclic voltammetry and controlled potential electrolysis studies demonstrate tha ...[more]

PMID: 28586133

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Project description:The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented. Atomic layer deposition (ALD) is adopted because it enables the synthesis of CoPi films with cobalt-to-phosphorous ratios between 1.4 and 1.9. It is shown that the pristine chemical composition of the CoPi film strongly influences its OER activity in the early stages of the activation process as well as after prolonged exposure to the electrolyte. The best performing CoPi catalyst, displaying a current density of 3.9 mA cm-2 at 1.8 V versus reversible hydrogen electrode and a Tafel slope of 155 mV/dec at pH 8.0, is selected for an in-depth study of the evolution of its electrochemical properties, chemical composition, and electrochemical active surface area (ECSA) during the activation process. Upon the increase of the number of CV cycles, the OER performance increases, in parallel with the development of a noncatalytic wave in the CV scan, which points out to the reversible oxidation of Co2+ species to Co3+ species. X-ray photoelectron spectroscopy and Rutherford backscattering measurements indicate that phosphorous progressively leaches out the CoPi film bulk upon prolonged exposure to the electrolyte. In parallel, the ECSA of the films increases by up to a factor of 40, depending on the initial stoichiometry. The ECSA of the activated CoPi films shows a universal linear correlation with the OER activity for the whole range of CoPi chemical composition. It can be concluded that the adoption of ALD in CoPi-based electrocatalysis enables, next to the well-established control over film growth and properties, to disclose the mechanisms behind the CoPi electrocatalyst activation.

Dataset Information

Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate.

Publications

Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate.

Similar Datasets

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