Quantum Efficiency of Charge Transfer Competing against Nonexponential Processes: The Case of Electron Transfer from CdS Nanorods to Hydrogenase

Utterback, James K.; Wilker, Molly B.; Mulder, David W.; King, Paul W.; Eaves, Joel D.; Dukovic, Gordana

doi:10.1021/acs.jpcc.8b09916

Title: Quantum Efficiency of Charge Transfer Competing against Nonexponential Processes: The Case of Electron Transfer from CdS Nanorods to Hydrogenase

Full Record
Other Related Research

Abstract

Photoexcited charge transfer from semiconductor nanocrystals to charge acceptors is a key step for photon energy conversion in semiconductor nanocrystal-based light-harvesting systems. Charge transfer competes against relaxation processes within the nanocrystals, and this competition determines the quantum efficiency of charge transfer. The quantum efficiency is a critical design element in photochemistry, but in nanocrystal-acceptor systems its extraction from experimental data is complicated by sample heterogeneity and intrinsically nonexponential excited-state decay pathways. In this manuscript, we systematically explore these complexities using TA spectroscopy over a broad range of timescales to probe electron transfer from CdS nanorods to the redox enzyme hydrogenase. To analyze the experimental data, we build a model that quantifies the quantum efficiency of charge transfer in the presence of competing, potentially nonexponential, relaxation processes. Our approach can be applied to calculate the efficiency of charge or energy transfer in any donor-acceptor system that exhibits nonexponential donor decay and any ensemble distribution in the number of acceptors, provided that donor relaxation and charge transfer can be described as independent, parallel decay pathways. We apply this analysis to our experimental system and unveil the connections between particle morphology and quantum efficiency. Our model predicts a finite quantum efficiency even whenmore »« less

Authors:

Utterback, James K. ^[1]; Wilker, Molly B. ^[2]; Mulder, David W. ^[3]; King, Paul W. ^[3]; Eaves, Joel D. ^[1]; Dukovic, Gordana ^[1]

Univ. of Colorado, Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); Luther College, Decorah, IA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Publication Date:: Thu Dec 06 00:00:00 EST 2018

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1492934

Report Number(s):: NREL/JA-2700-72605
Journal ID: ISSN 1932-7447

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 1; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; charge transfer; semiconductor nanocrystals; photon energy conversion; light harvesting

Citation Formats


                    Utterback, James K., Wilker, Molly B., Mulder, David W., King, Paul W., Eaves, Joel D., and Dukovic, Gordana. Quantum Efficiency of Charge Transfer Competing against Nonexponential Processes: The Case of Electron Transfer from CdS Nanorods to Hydrogenase.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b09916.

Copy to clipboard


                    Utterback, James K., Wilker, Molly B., Mulder, David W., King, Paul W., Eaves, Joel D., & Dukovic, Gordana. Quantum Efficiency of Charge Transfer Competing against Nonexponential Processes: The Case of Electron Transfer from CdS Nanorods to Hydrogenase.  United States.  https://doi.org/10.1021/acs.jpcc.8b09916

Copy to clipboard


                    Utterback, James K., Wilker, Molly B., Mulder, David W., King, Paul W., Eaves, Joel D., and Dukovic, Gordana. Thu .  
"Quantum Efficiency of Charge Transfer Competing against Nonexponential Processes: The Case of Electron Transfer from CdS Nanorods to Hydrogenase".  United States.  https://doi.org/10.1021/acs.jpcc.8b09916.  https://www.osti.gov/servlets/purl/1492934.

Copy to clipboard


                    
@article{osti_1492934,

  title        = {Quantum Efficiency of Charge Transfer Competing against Nonexponential Processes: The Case of Electron Transfer from CdS Nanorods to Hydrogenase},

  author       = {Utterback, James K. and Wilker, Molly B. and Mulder, David W. and King, Paul W. and Eaves, Joel D. and Dukovic, Gordana},

  abstractNote = {Photoexcited charge transfer from semiconductor nanocrystals to charge acceptors is a key step for photon energy conversion in semiconductor nanocrystal-based light-harvesting systems. Charge transfer competes against relaxation processes within the nanocrystals, and this competition determines the quantum efficiency of charge transfer. The quantum efficiency is a critical design element in photochemistry, but in nanocrystal-acceptor systems its extraction from experimental data is complicated by sample heterogeneity and intrinsically nonexponential excited-state decay pathways. In this manuscript, we systematically explore these complexities using TA spectroscopy over a broad range of timescales to probe electron transfer from CdS nanorods to the redox enzyme hydrogenase. To analyze the experimental data, we build a model that quantifies the quantum efficiency of charge transfer in the presence of competing, potentially nonexponential, relaxation processes. Our approach can be applied to calculate the efficiency of charge or energy transfer in any donor-acceptor system that exhibits nonexponential donor decay and any ensemble distribution in the number of acceptors, provided that donor relaxation and charge transfer can be described as independent, parallel decay pathways. We apply this analysis to our experimental system and unveil the connections between particle morphology and quantum efficiency. Our model predicts a finite quantum efficiency even when the mean recombination time diverges, as it does in CdS nanostructures with spatially separated electron-hole pairs that recombine with power-law dynamics. We contrast our approach to the widely used expressions for the quantum efficiency based on average lifetimes, which for our system overestimate the quantum efficiency. Furthermore, the approach developed here is straightforward to implement and should be applicable to a wide range of systems.},

  doi          = {10.1021/acs.jpcc.8b09916},

  journal      = {Journal of Physical Chemistry. C},

  number       = 1,

  volume       = 123,

  place        = {United States},

  year         = {Thu Dec 06 00:00:00 EST 2018},

  month        = {Thu Dec 06 00:00:00 EST 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcc.8b09916

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 18 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

The Kinetics of Electron Transfer from CdS Nanorods to the MoFe Protein of Nitrogenase

Journal Article Ruzicka, Jesse L. ; Pellows, Lauren M. ; Kallas, Hayden ; ... - Journal of Physical Chemistry. C

Combining the remarkable catalytic properties of redox enzymes with highly tunable light absorbing properties of semiconductor nanocrystals enables the light-driven catalysis of complex, multielectron redox reactions. This work focuses on systems that combine CdS nanorods (NRs) with the MoFe protein of nitrogenase to drive photochemical N₂ reduction. We used transient absorption spectroscopy (TAS) to examine the kinetics of electron transfer (ET) from CdS NRs to the MoFe protein. For CdS NRs with dimensions similar to those previously used for photochemical N₂ reduction, the rate constant for ET from CdS NRs competes with other electron relaxation processes, such that when amore »« less
https://doi.org/10.1021/acs.jpcc.2c02528

Full Text Available
Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H ₂ Generation

Journal Article Wilker, Molly B. ; Utterback, James K. ; Greene, Sophie ; ... - Journal of Physical Chemistry. C

Complexes of CdS nanorods and [FeFe] hydrogenase 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 themore »« less
Cited by 47
https://doi.org/10.1021/acs.jpcc.7b07229

Full Text Available
Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots

Journal Article Jia, Yanyan ; Chen, Jinquan ; Wu, Kaifeng ; ... - Chemical Science

Quantum confined semiconductor nanocrystals have emerged as a new class of materials for light harvesting and charge separation applications due to the ability to control their properties through rational design of their size, shape and composition. We report here a study of enhancing the quantum yield of methyl viologen (MV²⁺) photoreduction using colloidal quasi-type II CdSe/CdS core/shell quantum dots (QDs). The steady-state quantum yield of MV^+c radical generation, in the presence of thiols as sacrificial donors, increased monotonically with the CdS shell thickness within the studied thickness regime (0–4.7 CdS monolayers). Using ultrafast transient absorption and time-resolved photoluminescence decay spectroscopy,more »« less
Cited by 29
https://doi.org/10.1039/c6sc00192k

Full Text Available
Distance Dependence of Förster Resonance Energy Transfer Rates in 2D Perovskite Quantum Wells via Control of Organic Spacer Length

Journal Article Panuganti, Shobhana ; Besteiro, Lucas V. ; Vasileiadou, Eugenia S. ; ... - Journal of the American Chemical Society

Two-dimensional (2D) semiconductors are attractive candidates for a variety of optoelectronic applications owing to the unique electronic properties that arise from quantum confinement along a single dimension. Incorporating nonradiative mechanisms that enable directed migration of bound charge carriers, such as Forster resonance energy transfer (FRET), could boost device efficiencies provided that FRET rates outpace undesired relaxation pathways. However, predictive models for FRET between distinct 2D states are lacking, particularly with respect to the distance d between a donor and acceptor. We approach FRET in systems with binary mixtures of donor and acceptor 2D perovskite quantum wells (PQWs), and we syntheticallymore »« less
https://doi.org/10.1021/jacs.0c12441

Full Text Available
Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

Technical Report Pan, Shanlin

Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest thatmore »« less
https://doi.org/10.2172/1163882

Full Text Available

Similar Records