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Author Notes:

Correspondence: Mauricio Cattaneo, mcattaneo@fbqf.unt.edu.ar, Tianquan Lian, tlian@emory.edu, or Víctor S. Batista victor.batista@yale.edu

MC, TL, and VB contributed conception and design of the study. MC wrote the first draft of the manuscript. FG, HK, PV, LK, SG, AG, QL, and SW wrote sections of the manuscript. All authors contributed to manuscript revision, read, and approved the submitted version.

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Subjects:

Research Funding:

We thank Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) from Argentina for financial support.

MC is a member of the Research Career (CONICET).

VB acknowledges support from the Air Force Office of Scientific Research Grant No. FA9550-17-0198 and a generous allocation of computer time from NERSC and the high-performance computing facilities at Yale.

TL acknowledges support from the Air Force Office of Scientific Research Grant No. FA9550-18-1-0005.

Keywords:

  • CO2 reduction
  • SFG spectroscopy
  • disulfide
  • modified gold surfaces
  • rhenium complexes
  • spectroelectrochemistry

Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO<inf>2</inf> Reduction on Gold Electrodes

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Journal Title:

Frontiers in Chemistry

Volume:

Volume 8

Publisher:

, Pages 86-86

Type of Work:

Article | Final Publisher PDF

Abstract:

Heterogenization of homogenous catalysts on electrode surfaces provides a valuable approach for characterization of catalytic processes in operando conditions using surface selective spectroelectrochemistry methods. Ligand design plays a central role in the attachment mode and the resulting functionality of the heterogenized catalyst as determined by the orientation of the catalyst relative to the surface and the nature of specific interactions that modulate the redox properties under the heterogeneous electrode conditions. Here, we introduce new [Re(L)(CO)3Cl] catalysts for CO2 reduction with sulfur-based anchoring groups on a bipyridyl ligand, where L = 3,3′-disulfide-2,2′-bipyridine (SSbpy) and 3,3′-thio-2,2′-bipyridine (Sbpy). Spectroscopic and electrochemical analysis complemented by computational modeling at the density functional theory level identify the complex [Re(SSbpy)(CO)3Cl] as a multi-electron acceptor that combines the redox properties of both the rhenium tricarbonyl core and the disulfide functional group on the bipyridyl ligand. The first reduction at −0.85 V (vs. SCE) involves a two-electron process that breaks the disulfide bond, activating it for surface attachment. The heterogenized complex exhibits robust anchoring on gold surfaces, as probed by vibrational sum-frequency generation (SFG) spectroscopy. The binding configuration is normal to the surface, exposing the active site to the CO2 substrate in solution. The attachment mode is thus particularly suitable for electrocatalytic CO2 reduction.

Copyright information:

© 2020 Cattaneo, Guo, Kelly, Videla, Kiefer, Gebre, Ge, Liu, Wu, Lian and Batista.

This is an Open Access work distributed under the terms of the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/).
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