Electrocatalytic Properties of Binuclear Cu(II) Fused Porphyrins for Hydrogen Evolution

Diana Khusnutdinova, Brian Lawrence Wadsworth, Marco Flores, Anna Mary Beiler, Edgar Alejandro Reyes Cruz, Yegor Zenkov, Gary Moore

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Binuclear copper(II) porphyrins in which two copper(II) porphyrin macrocycles are doubly fused at the meso-beta positions are shown to be active electrocatalysts for the hydrogen evolution reaction (2H+ + 2e- → H2). 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 non-fused copper(II) porphyrin complex, the fused species is reduced at significantly less applied bias potentials (δE ~ 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-1. The enhancement in catalytic performance over analogous non-fused copper(II) porphyrins indicates extended macrocycles provide a structural motif and design element for preparing electrocatalysts that activate small molecules consequence to renewable energy.

Original languageEnglish (US)
JournalACS Catalysis
DOIs
StateAccepted/In press - Jan 1 2018

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Porphyrins
Copper
Hydrogen
Electrocatalysts
Photoelectron spectroscopy
Paramagnetic resonance
Protons
Metals
X rays
Catalysts
Molecules
Kinetics
Substrates

ASJC Scopus subject areas

  • Catalysis

Cite this

Khusnutdinova, D., Wadsworth, B. L., Flores, M., Beiler, A. M., Reyes Cruz, E. A., Zenkov, Y., & Moore, G. (Accepted/In press). Electrocatalytic Properties of Binuclear Cu(II) Fused Porphyrins for Hydrogen Evolution. ACS Catalysis. https://doi.org/10.1021/acscatal.8b01776

Electrocatalytic Properties of Binuclear Cu(II) Fused Porphyrins for Hydrogen Evolution. / Khusnutdinova, Diana; Wadsworth, Brian Lawrence; Flores, Marco; Beiler, Anna Mary; Reyes Cruz, Edgar Alejandro; Zenkov, Yegor; Moore, Gary.

In: ACS Catalysis, 01.01.2018.

Research output: Contribution to journalArticle

Khusnutdinova D, Wadsworth BL, Flores M, Beiler AM, Reyes Cruz EA, Zenkov Y et al. Electrocatalytic Properties of Binuclear Cu(II) Fused Porphyrins for Hydrogen Evolution. ACS Catalysis. 2018 Jan 1. https://doi.org/10.1021/acscatal.8b01776
Khusnutdinova, Diana ; Wadsworth, Brian Lawrence ; Flores, Marco ; Beiler, Anna Mary ; Reyes Cruz, Edgar Alejandro ; Zenkov, Yegor ; Moore, Gary. / Electrocatalytic Properties of Binuclear Cu(II) Fused Porphyrins for Hydrogen Evolution. In: ACS Catalysis. 2018.
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