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Title: Orbital-Resolved Imaging of the Adsorbed State of Pyridine on GaP(110) Identifies Sites Susceptible to Nucleophilic Attack

Abstract

Artificial photosynthesis by photoelectrocatalytic CO2 reduction is dependent, as is natural photosynthesis, on interfacial electron transfer to couple light excitation energy to reaction centers. For heterogeneous systems, in the context of frontier orbital theory, artificial reaction centers are defined through the interactions of filled and empty orbitals within a few electron volts of the Fermi energy of the adsorbate complex. Here we report a scanning tunneling microscopy (STM) and density functional theory investigation of the orbital-resolved adsorption state defining the dative bonding interaction between a III-V semiconductor surface [GaP(110)] and a N containing heteroaromatic (pyridine). This system was selected for its relevance to photoelectrocatalysis utilizing heteroaromatic co-catalysts, which has been reported to yield highly selective CO2 reduction to fuels. By examining the distribution of unoccupied molecular orbitals, we show that STM images can be used to positively identify the sites on pyridine susceptible to nucleophilic attack, consistent with frontier orbital theory. Furthermore, this indicates that STM can be used to explore the local reaction centers of adsorbed ambidentate electrophiles and nucleophiles relevant to artificial photosynthesis, and more broadly to generate critical mechanistic information for various heterogeneous acid-base reactions.

Authors:
 [1];  [1];  [2];  [3];  [4];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Princeton Univ., NJ (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Univ. of Naples Federico II (Italy)
  4. Univ. of Nebraska, Lincoln, NE (United States)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1855722
Report Number(s):
DOE-PU-0012455-3
Journal ID: ISSN 1932-7447; FA9550-10-1-0572
Grant/Contract Number:  
SC0012455
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 52; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; pyridine; semiconductor; imaging; STM; adsorption; molecules; tunneling; scanning tunneling microscopy

Citation Formats

Kronawitter, Coleman X., Lessio, Martina, Zahl, Percy, Muñoz-García, Ana B., Sutter, Peter, Carter, Emily A., and Koel, Bruce E. Orbital-Resolved Imaging of the Adsorbed State of Pyridine on GaP(110) Identifies Sites Susceptible to Nucleophilic Attack. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b08659.
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Kronawitter, Coleman X., Lessio, Martina, Zahl, Percy, Muñoz-García, Ana B., Sutter, Peter, Carter, Emily A., & Koel, Bruce E. Orbital-Resolved Imaging of the Adsorbed State of Pyridine on GaP(110) Identifies Sites Susceptible to Nucleophilic Attack. United States. https://doi.org/10.1021/acs.jpcc.5b08659
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Kronawitter, Coleman X., Lessio, Martina, Zahl, Percy, Muñoz-García, Ana B., Sutter, Peter, Carter, Emily A., and Koel, Bruce E. Thu . "Orbital-Resolved Imaging of the Adsorbed State of Pyridine on GaP(110) Identifies Sites Susceptible to Nucleophilic Attack". United States. https://doi.org/10.1021/acs.jpcc.5b08659. https://www.osti.gov/servlets/purl/1855722.
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@article{osti_1855722,
title = {Orbital-Resolved Imaging of the Adsorbed State of Pyridine on GaP(110) Identifies Sites Susceptible to Nucleophilic Attack},
author = {Kronawitter, Coleman X. and Lessio, Martina and Zahl, Percy and Muñoz-García, Ana B. and Sutter, Peter and Carter, Emily A. and Koel, Bruce E.},
abstractNote = {Artificial photosynthesis by photoelectrocatalytic CO2 reduction is dependent, as is natural photosynthesis, on interfacial electron transfer to couple light excitation energy to reaction centers. For heterogeneous systems, in the context of frontier orbital theory, artificial reaction centers are defined through the interactions of filled and empty orbitals within a few electron volts of the Fermi energy of the adsorbate complex. Here we report a scanning tunneling microscopy (STM) and density functional theory investigation of the orbital-resolved adsorption state defining the dative bonding interaction between a III-V semiconductor surface [GaP(110)] and a N containing heteroaromatic (pyridine). This system was selected for its relevance to photoelectrocatalysis utilizing heteroaromatic co-catalysts, which has been reported to yield highly selective CO2 reduction to fuels. By examining the distribution of unoccupied molecular orbitals, we show that STM images can be used to positively identify the sites on pyridine susceptible to nucleophilic attack, consistent with frontier orbital theory. Furthermore, this indicates that STM can be used to explore the local reaction centers of adsorbed ambidentate electrophiles and nucleophiles relevant to artificial photosynthesis, and more broadly to generate critical mechanistic information for various heterogeneous acid-base reactions.},
doi = {10.1021/acs.jpcc.5b08659},
journal = {Journal of Physical Chemistry. C},
number = 52,
volume = 119,
place = {United States},
year = {Thu Dec 03 00:00:00 EST 2015},
month = {Thu Dec 03 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acs.jpcc.5b08659
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    Works referencing / citing this record:

    Hydride Shuttle Formation and Reaction with CO 2 on GaP(110)
    journal, April 2018

    • Lessio, Martina; Senftle, Thomas P.; Carter, Emily A.
    • ChemSusChem, Vol. 11, Issue 9
    • DOI: 10.1002/cssc.201800037
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