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Immobilized Cobalt Bis(benzenedithiolate) Complexes: Exceptionally Active Heterogeneous Electrocatalysts for Dihydrogen Production from Mildly Acidic Aqueous Solutions
journal contribution
posted on 2017-09-21, 15:05 authored by Shawn C. Eady, Molly M. MacInnes, Nicolai LehnertA series of cobalt
bis(benzenedithiolate) complexes with varying benzenedithiolate (general
abbreviation: bdt2–) ring substitutions (S2C6X42–) were prepared and
adsorbed on inexpensive electrodes composed of (a) reduced graphene
oxide (RGO) electrodeposited on fluorine-doped tin oxide (FTO) and
(b) highly ordered pyrolytic graphite (HOPG). The catalyst-adsorbed
electrodes are characterized by X-ray photoelectron spectroscopy.
Catalyst loading across the ligand series improved notably with increasing
halide substitution [from 2.7 × 10–11 mol cm–2 for TBA[Co(S2C6H4)2] (1) to 6.22 × 10–10 mol cm–2 for TBA[Co(S2C6Cl4)2] (3)] and increasing ring
size of the benzenedithiolate ligand [up to 3.10 × 10–9 mol cm–2 for TBA[Co(S2C10H6)2] (6)]. Electrocatalytic analysis
of the complexes immobilized on HOPG elicits a reductive current response
indicative of dihydrogen generation in the presence of mildly acidic
aqueous solutions (pH 2–4) of trifluoroacetic acid, with overpotentials
of around 0.5 V versus SHE (measured vs platinum). Rate constant (kobs) estimates resulting from cyclic voltammetry
analysis range from 24 to 230 s–1 with the maximum kobs for TBA[Co(S2C6H2Cl2)2] (2) at an overpotential
of 0.59 V versus platinum. Controlled-potential electrolysis studies
performed in 0.5 M H2SO4 at −0.5 V versus
SHE show impressive initial rate constants of over 500 s–1 under bulk electrolysis conditions; however, steady catalyst deactivation
over an 8 h period is observed, with turnover numbers reaching 9.1
× 106. Electrolysis studies reveal that halide substitution
is a central factor in improving the turnover stability, whereas the
ring size is less of a factor in optimizing the long-term stability
of the heterogeneous catalyst manifolds. Catalyst deactivation is
likely caused by catalyst desorption from the electrode surfaces.
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ligandfactorbulk electrolysis conditionsmolstabilityring sizeseriesk obselectrodeRGO8 h periodSHETBAHOPGcmFTOcatalyst deactivationoverpotentialClcyclic voltammetry analysis range0.5 M H 2Controlled-potential electrolysis studiesfluorine-doped tin oxidecomplexhalide substitutionMildly Acidic Aqueous SolutionsX-ray photoelectron spectroscopybenzenedithiolate
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