The Role of Surface-Capping Ligands in Photoexcited Electron Transfer Between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H2 Generation

Molly B. Wilker, James K. Utterback, Sophie Greene, Katherine A. Brown, David W. Mulder, Paul W. King, Gordana Dukovic

Research output: Contribution to journalArticlepeer-review

53 Scopus Citations

Abstract

Complexes of CdS nanorods and [FeFe] hydrogenase I from Clostridium acetobutylicum have been shown to photochemically produce H2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggesting that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.

Original languageAmerican English
Pages (from-to)741-750
Number of pages10
JournalJournal of Physical Chemistry C
Volume122
Issue number1
DOIs
StatePublished - 11 Jan 2018

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

NREL Publication Number

  • NREL/JA-2700-68946

Keywords

  • hydrogenase
  • ligands
  • nanocrystals

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