Electrocatalytic Properties of Binuclear Cu(II) Fused
Porphyrins for Hydrogen Evolution
Diana Khusnutdinova
Brian L. Wadsworth
Marco Flores
Anna M. Beiler
Edgar A. Reyes Cruz
Yegor Zenkov
Gary F. Moore
10.1021/acscatal.8b01776.s001
https://acs.figshare.com/articles/journal_contribution/Electrocatalytic_Properties_of_Binuclear_Cu_II_Fused_Porphyrins_for_Hydrogen_Evolution/7140359
Binuclear
copper(II) porphyrins in which two copper(II) porphyrin
macrocycles are doubly fused at the <i>meso</i>-beta positions
are shown to be active electrocatalysts for the hydrogen evolution
reaction (2H<sup>+</sup> + 2e<sup>–</sup> → H<sub>2</sub>). Structural characterization, including use of electron paramagnetic
resonance and X-ray photoelectron spectroscopies, verifies the fused
species contains two copper(II) metal centers in its resting state.
In comparison to the nonfused copper(II) porphyrin complex, the fused
species is reduced at significantly less applied bias potentials (Δ<i>E</i><sub>1/2</sub> ∼ 570 mV for the first reduction
process). Electrochemical characterization in the presence of substrate
protons confirms the production of hydrogen with near-unity Faradaic
efficiency, and kinetic analysis shows the catalyst achieves a maximum
turnover frequency above 2 000 000 s<sup>–1</sup>. The enhancement in catalytic performance over analogous nonfused
copper(II) porphyrins indicates extended macrocycles provide an advantageous
structural motif and design element for preparing electrocatalysts
that activate small molecules of consequence to renewable energy.
2018-08-14 00:00:00
Electrocatalytic Properties
turnover frequency
X-ray photoelectron spectroscopies
beta positions
2 000 000
near-unity Faradaic efficiency
nonfused
electrocatalyst
macrocycle
Structural characterization
porphyrin
substrate protons
reduction process
species
design element
Electrochemical characterization
Binuclear