Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Ultrafast terahertz spectroscopy provides insight into charge transfer efficiency and dynamics in artificial photosynthesis

Journal Article · · Photosynthesis Research
 [1];  [2];  [2];  [2];  [2]
  1. Yale Univ., New Haven, CT (United States); Yale University
  2. Yale Univ., New Haven, CT (United States)
+ Show Author Affiliations
Terahertz (THz) spectroscopy provides a noncontact method to measure the ultrafast dynamics and photoconductivity of mobile carriers in semiconducting materials. This has proven useful in studying artificial photosynthesis devices which use semiconductor photoelectrodes. In this work, we present a brief introduction to optical-pump THz-probe (OPTP) spectroscopy, a technique that provides unique and useful insight into interfacial electron transfer (from the surface-attached dye to the conduction band of the semiconductor) in dye-sensitized photoelectrochemical cells. Compared with more familiar methods like visible transient absorption spectroscopy, OPTP spectroscopy stands out in offering both sub-picosecond time resolution as well as sensitivity to mobile carriers (electrons and holes) in the semiconductor portion of artificial photosynthesis devices. The mobile carriers are crucial to device performance as only they pass to the other half cell to complete the reaction. In order to highlight these advantages and illustrate the types of questions OPTP spectroscopy can address, we discuss three case studies. In the first, OPTP spectroscopy is used to measure the injection rates from a set of six different dyes, revealing the effect of the energetics and lifetimes of the dye excited states on interfacial electron transfer. The subsequent case studies investigate the influence of varying the moieties which bind to the surface (anchors), as well as the moieties that connect the chromophore with these anchors (linkers). OPTP spectroscopy was used to measure the interfacial electron transfer rate as these moieties were varied.
Research Organization:
Yale Univ., New Haven, CT (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
FG02-07ER15909
OSTI ID:
1812302
Journal Information:
Photosynthesis Research, Journal Name: Photosynthesis Research Vol. 151; ISSN 0166-8595
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English

References (36)

Ground and Excited State Electronic Properties of Halogenated Tetraarylporphyrins: Tuning the Building Blocks for Porphyrin-based Photonic Devices journal February 1999
Porphyrin Sensitizers with Donor Structural Engineering for Superior Performance Dye-Sensitized Solar Cells and Tandem Solar Cells for Water Splitting Applications journal December 2016
Short-lived excited triplet states studied by time-resolved EPR spectroscopy journal October 2003
A Terahertz-Transparent Electrochemical Cell for In Situ Terahertz Spectroelectrochemistry journal February 2018
Terahertz Spectroscopy of Emerging Materials journal September 2020
Size-Dependent Ultrafast Charge Carrier Dynamics of WO 3 for Photoelectrochemical Cells journal June 2016
Frequency-Dependent Terahertz Transient Photoconductivity of Mesoporous SnO 2 Films journal July 2017
Linker Length-Dependent Electron-Injection Dynamics of Trimesitylporphyrins on SnO 2 Films journal October 2017
Direct Interfacial Electron Transfer from High-Potential Porphyrins into Semiconductor Surfaces: A Comparison of Linkers and Anchoring Groups journal December 2017
Charge Transfer Dynamics in Aqueous Dye-Sensitized Photoelectrochemical Cells: Implications for Water Splitting Efficiency journal December 2018
Two-Dimensional MXenes Mo 2 Ti 2 C 3 T z and Mo 2 TiC 2 T z : Microscopic Conductivity and Dynamics of Photoexcited Carriers journal January 2020
Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer journal December 2016
Interfacial Electron Transfer into Functionalized Crystalline Polyoxotitanate Nanoclusters journal May 2012
Photoelectrochemical Hole Injection Revealed in Polyoxotitanate Nanocrystals Functionalized with Organic Adsorbates journal November 2014
Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells journal September 2016
Metal–Organic Framework Photoconductivity via Time-Resolved Terahertz Spectroscopy journal June 2019
Explaining the Enhanced Photocatalytic Activity of Degussa P25 Mixed-Phase TiO 2 Using EPR journal May 2003
Bridge-Assisted Ultrafast Interfacial Electron Transfer to Nanocrystalline SnO 2 Thin Films journal December 2003
Role of Adsorption Structures of Zn-Porphyrin on TiO 2 in Dye-Sensitized Solar Cells Studied by Sum Frequency Generation Vibrational Spectroscopy and Ultrafast Spectroscopy journal March 2013
Modular Assembly of High-Potential Zinc Porphyrin Photosensitizers Attached to TiO 2 with a Series of Anchoring Groups journal July 2013
Electron Injection Dynamics from Photoexcited Porphyrin Dyes into SnO 2 and TiO 2 Nanoparticles journal October 2013
High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework journal October 2018
The role of adsorbates in the green emission and conductivity of zinc oxide journal May 2019
A visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst journal January 2011
In situ probe of photocarrier dynamics in water-splitting hematite (α-Fe2O3) electrodes journal January 2012
Comparison of silatrane, phosphonic acid, and carboxylic acid functional groups for attachment of porphyrin sensitizers to TiO2 in photoelectrochemical cells journal January 2013
Spectroscopic properties of electrochemically populated electronic states in nanostructured TiO2 films: anatase versus rutile journal January 2013
Band energies of nanoparticle semiconductor electrodes determined by spectroelectrochemical measurements of free electrons journal January 2015
Molecular design of light-harvesting photosensitizers: effect of varied linker conjugation on interfacial electron transfer journal January 2016
Ultrafast carrier dynamics in BiVO 4 thin film photoanode material: interplay between free carriers, trapped carriers and low-frequency lattice vibrations journal January 2016
Anchoring groups for photocatalytic water oxidation on metal oxide surfaces journal January 2017
Photophysics and spectroscopy of the higher electronic states of zinc metalloporphyrins: a theoretical and experimental study journal January 2006
The study of charge carrier kinetics in semiconductors by microwave conductivity measurements journal November 1986
1-(3′-amino)propylsilatrane derivatives as covalent surface linkers to nanoparticulate metal oxide films for use in photoelectrochemical cells journal November 2009
Transient photoconductivity in GaAs as measured by time-resolved terahertz spectroscopy journal December 2000
Synthesis, Spectra and Photophysics of some Free Base Tetrafluoroalkyl and Tetrafluoroaryl Porphyrins with Potential Applications in Imaging¶ journal March 2002

Similar Records

Linker Length-Dependent Electron-Injection Dynamics of Trimesitylporphyrins on SnO2 Films
Journal Article · Wed Sep 20 20:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1483383
All-vanadium photoelectrochemical storage cells using dye sensitized geometry-enhanced TiO{sub 2} nanobelts
Journal Article · Thu Dec 14 23:00:00 EST 2017 · Materials Research Bulletin · OSTI ID:22730499
Optical-pump–terahertz-probe spectroscopy in high magnetic fields with kHz single-shot detection
Journal Article · Thu Feb 29 19:00:00 EST 2024 · Review of Scientific Instruments · OSTI ID:2578434

Related Subjects

59 BASIC BIOLOGICAL SCIENCES
artificial photosynthesis
charge transfer
terahertz spectroscopy
ultrafast