@article{c741a8d4a2f84430b6f3042aec47ec08,
title = "Electrocatalytic Properties of Binuclear Cu(II) Fused Porphyrins for Hydrogen Evolution",
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 nonfused copper(II) porphyrin complex, the fused species is reduced at significantly less applied bias potentials (ΔE1/2 ∼ 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 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.",
author = "Diana Khusnutdinova and Wadsworth, {Brian L.} and Marco Flores and Beiler, {Anna M.} and {Reyes Cruz}, {Edgar A.} and Yegor Zenkov and Moore, {Gary F.}",
note = "Funding Information: XPS experiments were performed at the LeRoy Eyring Center for Solid State Science. We thank Timothy Karcher for assistance with XPS data collection and Marco Flores in the Electron Paramagnetic Resonance Facility for assistance with EPR data collection. NMR studies were performed using the Magnetic Resonance Research Center at Arizona State University. This material is based upon work supported through the College of Liberal Arts and Sciences of Arizona State University, the Biodesign Institute Center for Applied Structural Discovery (CASD), and ASU LightWorks. B.L.W. and A.M.B. were supported by an IGERT-SUN fellowship funded by the National Science Foundation (1144616). A.M.B received additional support from the Phoenix Chapter of the ARCS Foundation and the P.E.O Scholar Award. D.K. acknowledges support from ASU LightWorks under the Technology and Research Initiative Funds. Funding Information: XPS experiments were performed at the LeRoy Eyring Center for Solid State Science. We thank Timothy Karcher for assistance with XPS data collection and Marco Flores in the Electron Paramagnetic Resonance Facility for assistance with EPR data collection. NMR studies were performed using the Magnetic Resonance Research Center at Arizona State University. This material is based upon work supported through the College of Liberal Arts and Sciences of Arizona State University the Biodesign Institute Center for Applied Structural Discovery (CASD) and ASU LightWorks. B.L.W. and A.M.B. were supported by an IGERT-SUN fellowship funded by the National Science Foundation (1144616). A.M.B received additional support from the Phoenix Chapter of the ARCS Foundation and the P.E.O Scholar Award. D.K. acknowledges support from ASU LightWorks under the Technology and Research Initiative Funds. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",
year = "2018",
month = oct,
day = "5",
doi = "10.1021/acscatal.8b01776",
language = "English (US)",
volume = "8",
pages = "9888--9898",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "10",
}