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Title: Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis

Abstract

Plasmonic metal nanoparticles enhance chemical reactions on their surface when illuminated with light of particular frequencies. It has been shown that these processes are driven by excitation of localized surface plasmon resonance (LSPR). The interaction of LSPR with adsorbate orbitals can lead to the injection of energized charge carriers into the adsorbate, which can result in chemical transformations. The mechanism of the charge injection process (and role of LSPR) is not well understood. Here we shed light on the specifics of this mechanism by coupling optical characterization methods, mainly wavelength-dependent Stokes and anti-Stokes SERS, with kinetic analysis of photocatalytic reactions in an Ag nanocube–methylene blue plasmonic system. We propose that localized LSPR-induced electric fields result in a direct charge transfer within the molecule–adsorbate system. Lastly, these observations provide a foundation for the development of plasmonic catalysts that can selectively activate targeted chemical bonds, since the mechanism allows for tuning plasmonic nanomaterials in such a way that illumination can selectively enhance desired chemical pathways.

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1242978
Grant/Contract Number:  
FG02-05ER15686
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; chemical sciences; catalysis; physical chemistry

Citation Formats

Boerigter, Calvin, Campana, Robert, Morabito, Matthew, and Linic, Suljo. Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis. United States: N. p., 2016. Web. doi:10.1038/ncomms10545.
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Boerigter, Calvin, Campana, Robert, Morabito, Matthew, & Linic, Suljo. Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis. United States. doi:10.1038/ncomms10545.
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Boerigter, Calvin, Campana, Robert, Morabito, Matthew, and Linic, Suljo. Thu . "Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis". United States. doi:10.1038/ncomms10545. https://www.osti.gov/servlets/purl/1242978.
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@article{osti_1242978,
title = {Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis},
author = {Boerigter, Calvin and Campana, Robert and Morabito, Matthew and Linic, Suljo},
abstractNote = {Plasmonic metal nanoparticles enhance chemical reactions on their surface when illuminated with light of particular frequencies. It has been shown that these processes are driven by excitation of localized surface plasmon resonance (LSPR). The interaction of LSPR with adsorbate orbitals can lead to the injection of energized charge carriers into the adsorbate, which can result in chemical transformations. The mechanism of the charge injection process (and role of LSPR) is not well understood. Here we shed light on the specifics of this mechanism by coupling optical characterization methods, mainly wavelength-dependent Stokes and anti-Stokes SERS, with kinetic analysis of photocatalytic reactions in an Ag nanocube–methylene blue plasmonic system. We propose that localized LSPR-induced electric fields result in a direct charge transfer within the molecule–adsorbate system. Lastly, these observations provide a foundation for the development of plasmonic catalysts that can selectively activate targeted chemical bonds, since the mechanism allows for tuning plasmonic nanomaterials in such a way that illumination can selectively enhance desired chemical pathways.},
doi = {10.1038/ncomms10545},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {1}
}
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DOI:  10.1038/ncomms10545
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Works referenced in this record:

Surface plasmon resonance-mediated photocatalysis by noble metal-based composites under visible light
journal, January 2012

  • Zhou, Xuemei; Liu, Gang; Yu, Jiaguo
  • Journal of Materials Chemistry, Vol. 22, Issue 40
  • DOI: 10.1039/c2jm31902k

Tuning Selectivity in Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu Oxidation State
journal, March 2013

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy
journal, November 2011

  • Linic, Suljo; Christopher, Phillip; Ingram, David B.
  • Nature Materials, Vol. 10, Issue 12
  • DOI: 10.1038/nmat3151

Hot Electrons Do the Impossible: Plasmon-Induced Dissociation of H 2 on Au
journal, December 2012

  • Mukherjee, Shaunak; Libisch, Florian; Large, Nicolas
  • Nano Letters, Vol. 13, Issue 1
  • DOI: 10.1021/nl303940z

Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures
journal, May 2011

  • Christopher, Phillip; Xin, Hongliang; Linic, Suljo
  • Nature Chemistry, Vol. 3, Issue 6
  • DOI: 10.1038/nchem.1032

Quantum plasmon resonances of individual metallic nanoparticles
journal, March 2012

  • Scholl, Jonathan A.; Koh, Ai Leen; Dionne, Jennifer A.
  • Nature, Vol. 483, Issue 7390
  • DOI: 10.1038/nature10904

Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures
journal, October 2012

  • Christopher, Phillip; Xin, Hongliang; Marimuthu, Andiappan
  • Nature Materials, Vol. 11, Issue 12
  • DOI: 10.1038/nmat3454

Hot-Electron-Induced Dissociation of H 2 on Gold Nanoparticles Supported on SiO 2
journal, December 2013

  • Mukherjee, Shaunak; Zhou, Linan; Goodman, Amanda M.
  • Journal of the American Chemical Society, Vol. 136, Issue 1
  • DOI: 10.1021/ja411017b

Photodecomposition of Diazanaphthalenes Adsorbed on Silver Colloid Surfaces
journal, April 2000

  • Jeong, Dae Hong; Jang, Nak Han; Suh, Jung Sang
  • The Journal of Physical Chemistry B, Vol. 104, Issue 15
  • DOI: 10.1021/jp993814e

Vibrational excitation in molecule–surface collisions due to temporary negative molecular ion formation
journal, December 1983

  • Gadzuk, J. W.
  • The Journal of Chemical Physics, Vol. 79, Issue 12
  • DOI: 10.1063/1.445742

Photochemical transformations on plasmonic metal nanoparticles
journal, May 2015

  • Linic, Suljo; Aslam, Umar; Boerigter, Calvin
  • Nature Materials, Vol. 14, Issue 6
  • DOI: 10.1038/nmat4281

Adsorbate Photochemistry on a Colloid Surface:  Phthalazine on Silver
journal, January 1996

  • Suh, Jung Sang; Jang, Nak Han; Jeong, Dae Hong
  • The Journal of Physical Chemistry, Vol. 100, Issue 2
  • DOI: 10.1021/jp952184n

Photochemical decomposition at colloid surfaces
journal, February 1993

  • Suh, Jung Sang; Moskovits, Martin; Shakhesemampour, Jalal
  • The Journal of Physical Chemistry, Vol. 97, Issue 8
  • DOI: 10.1021/j100110a034

Electromagnetic fields around silver nanoparticles and dimers
journal, January 2004

  • Hao, Encai; Schatz, George C.
  • The Journal of Chemical Physics, Vol. 120, Issue 1, p. 357-366
  • DOI: 10.1063/1.1629280

Self-Organized Silver Nanoparticles for Three-Dimensional Plasmonic Crystals
journal, November 2008

  • Tao, Andrea R.; Ceperley, Daniel P.; Sinsermsuksakul, Prasert
  • Nano Letters, Vol. 8, Issue 11
  • DOI: 10.1021/nl802877h

Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications
journal, June 2011

  • Rycenga, Matthew; Cobley, Claire M.; Zeng, Jie
  • Chemical Reviews, Vol. 111, Issue 6
  • DOI: 10.1021/cr100275d

Localized Surface Plasmon Resonance Spectroscopy of Single Silver Nanocubes
journal, October 2005

  • Sherry, Leif J.; Chang, Shih-Hui; Schatz, George C.
  • Nano Letters, Vol. 5, Issue 10
  • DOI: 10.1021/nl0515753

Quantum Description of the Plasmon Resonances of a Nanoparticle Dimer
journal, February 2009

  • Zuloaga, Jorge; Prodan, Emil; Nordlander, Peter
  • Nano Letters, Vol. 9, Issue 2
  • DOI: 10.1021/nl803811g

Quantum Plasmon Resonances Controlled by Molecular Tunnel Junctions
journal, March 2014

Bridging quantum and classical plasmonics with a quantum-corrected model
journal, January 2012

  • Esteban, Ruben; Borisov, Andrei G.; Nordlander, Peter
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1806

Revealing the quantum regime in tunnelling plasmonics
journal, November 2012

  • Savage, Kevin J.; Hawkeye, Matthew M.; Esteban, Rubén
  • Nature, Vol. 491, Issue 7425
  • DOI: 10.1038/nature11653

A generalized non-local optical response theory for plasmonic nanostructures
journal, May 2014

  • Mortensen, N. A.; Raza, S.; Wubs, M.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4809

Pyridine on Colloidal Silver. Polarization of Surface Studied by Surface-Enhanced Raman Scattering and Density Functional Theory Methods
journal, February 2010

  • Kaczor, Agnieszka; Malek, Kamilla; Baranska, Malgorzata
  • The Journal of Physical Chemistry C, Vol. 114, Issue 9
  • DOI: 10.1021/jp912071a

Surface-enhanced Raman scattering of methylene blue adsorbed on cap-shaped silver nanoparticles
journal, October 2007

Surface-Enhanced Resonance Raman (SERR) Spectra of Methylene Blue Adsorbed on a Silver Electrode
journal, May 2003

  • Nicolai, Silvia H. A.; Rubim, Joel C.
  • Langmuir, Vol. 19, Issue 10
  • DOI: 10.1021/la034076v

Collective Theory for Surface Enhanced Raman Scattering
journal, August 1996

On the chemical mechanism of surface enhanced Raman scattering: Experiment and theory
journal, March 1998

  • Kambhampati, Patanjali; Child, C. M.; Foster, Michelle C.
  • The Journal of Chemical Physics, Vol. 108, Issue 12
  • DOI: 10.1063/1.475909

Vibrational pumping in surface enhanced Raman scattering (SERS)
journal, January 2008

  • Maher, R. C.; Galloway, C. M.; Le Ru, E. C.
  • Chemical Society Reviews, Vol. 37, Issue 5
  • DOI: 10.1039/b707870f

Population Pumping of Excited Vibrational States by Spontaneous Surface-Enhanced Raman Scattering
journal, April 1996

Can surface-enhanced Raman scattering serve as a channel for strong optical pumping?
journal, July 2000

  • Haslett, T. L.; Tay, L.; Moskovits, M.
  • The Journal of Chemical Physics, Vol. 113, Issue 4
  • DOI: 10.1063/1.481952

Design of Plasmonic Platforms for Selective Molecular Sensing Based on Surface-Enhanced Raman Spectroscopy
journal, April 2012

  • Marimuthu, A.; Christopher, Phillip; Linic, Suljo
  • The Journal of Physical Chemistry C, Vol. 116, Issue 17
  • DOI: 10.1021/jp301443y

Second enhancement in surface-enhanced resonance Raman scattering revealed by an analysis of anti-Stokes and Stokes Raman spectra
journal, August 2007

Mode specific vibrational kinetics after intramolecular electron transfer studied by picosecond anti-Stokes Raman spectroscopy
journal, October 1999

Characterizing the Kinetics of Nanoparticle-Catalyzed Reactions by Surface-Enhanced Raman Scattering
journal, July 2012

  • Joseph, Virginia; Engelbrekt, Christian; Zhang, Jingdong
  • Angewandte Chemie International Edition, Vol. 51, Issue 30
  • DOI: 10.1002/anie.201203526

Plasmon-Assisted Indirect Light Absorption Engineering in Small Transition Metal Catalyst Nanoparticles
journal, August 2015

  • Antosiewicz, Tomasz J.; Wadell, Carl; Langhammer, Christoph
  • Advanced Optical Materials, Vol. 3, Issue 11
  • DOI: 10.1002/adom.201500284

Heterogenous Catalysis Mediated by Plasmon Heating
journal, December 2009

  • Adleman, James R.; Boyd, David A.; Goodwin, David G.
  • Nano Letters, Vol. 9, Issue 12
  • DOI: 10.1021/nl902711n

Large-Scale Synthesis of Silver Nanocubes: The Role of HCl in Promoting Cube Perfection and Monodispersity
journal, March 2005

  • Im, Sang Hyuk; Lee, Yun Tack; Wiley, Benjamin
  • Angewandte Chemie International Edition, Vol. 44, Issue 14
  • DOI: 10.1002/anie.200462208

Meep: A flexible free-software package for electromagnetic simulations by the FDTD method
journal, March 2010

  • Oskooi, Ardavan F.; Roundy, David; Ibanescu, Mihai
  • Computer Physics Communications, Vol. 181, Issue 3, p. 687-702
  • DOI: 10.1016/j.cpc.2009.11.008

Optical properties of metallic films for vertical-cavity optoelectronic devices
journal, January 1998

  • Rakić, Aleksandar D.; Djurišić, Aleksandra B.; Elazar, Jovan M.
  • Applied Optics, Vol. 37, Issue 22, p. 5271-5283
  • DOI: 10.1364/AO.37.005271

Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method
journal, June 2010

Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012

    [ × clear filter / sort ]

    Works referencing / citing this record:

    Nanostructured organic semiconductor films for molecular detection with surface-enhanced Raman spectroscopy
    journal, August 2017

    • Yilmaz, Mehmet; Babur, Esra; Ozdemir, Mehmet
    • Nature Materials, Vol. 16, Issue 9
    • DOI: 10.1038/nmat4957

    Atomic dispensers for thermoplasmonic control of alkali vapor pressure in quantum optical applications
    journal, May 2019

    • Rusimova, Kristina R.; Slavov, Dimitar; Pradaux-Caggiano, Fabienne
    • Nature Communications, Vol. 10, Issue 1
    • DOI: 10.1038/s41467-019-10158-4

    Synthesis of Au@TiO 2 core–shell nanoparticles with tunable structures for plasmon-enhanced photocatalysis
    journal, January 2019

    • Chen, Tian-Ming; Xu, Ge-Yang; Ren, He
    • Nanoscale Advances, Vol. 1, Issue 11
    • DOI: 10.1039/c9na00548j

    Self-Z-scheme plasmonic tungsten oxide nanowires for boosting ethanol dehydrogenation under UV-visible light irradiation
    journal, January 2019

    • Lu, Changhai; Li, Juan; Chen, Guanying
    • Nanoscale, Vol. 11, Issue 27
    • DOI: 10.1039/c9nr03741a

    Nanostructured organic semiconductor films for molecular detection with surface-enhanced Raman spectroscopy
    journal, August 2017

    • Yilmaz, Mehmet; Babur, Esra; Ozdemir, Mehmet
    • Nature Materials, Vol. 16, Issue 9
    • DOI: 10.1038/nmat4957

    Atomic dispensers for thermoplasmonic control of alkali vapor pressure in quantum optical applications
    journal, May 2019

    • Rusimova, Kristina R.; Slavov, Dimitar; Pradaux-Caggiano, Fabienne
    • Nature Communications, Vol. 10, Issue 1
    • DOI: 10.1038/s41467-019-10158-4

    First-principles study on charge transfer in an actinide-containing superatom from surface-enhanced Raman scattering
    journal, January 2017

    • Gao, Yang; Jiang, Wanrun; Chen, Lei
    • Journal of Materials Chemistry C, Vol. 5, Issue 4
    • DOI: 10.1039/c6tc04865j

    Synthesis of Au@TiO 2 core–shell nanoparticles with tunable structures for plasmon-enhanced photocatalysis
    journal, January 2019

    • Chen, Tian-Ming; Xu, Ge-Yang; Ren, He
    • Nanoscale Advances, Vol. 1, Issue 11
    • DOI: 10.1039/c9na00548j

    Self-Z-scheme plasmonic tungsten oxide nanowires for boosting ethanol dehydrogenation under UV-visible light irradiation
    journal, January 2019

    • Lu, Changhai; Li, Juan; Chen, Guanying
    • Nanoscale, Vol. 11, Issue 27
    • DOI: 10.1039/c9nr03741a

    Quantum-Sized Metal Catalysts for Hot-Electron-Driven Chemical Transformation
    journal, August 2018

    Tracing the Origin of Visible Light Enhanced Oxygen Evolution Reaction
    journal, December 2018

    • Cai, Chao; Han, Shaobo; Caiyang, Weinan
    • Advanced Materials Interfaces, Vol. 6, Issue 3
    • DOI: 10.1002/admi.201801543

    Efficiency and Bond Selectivity in Plasmon-Induced Photochemistry
    journal, June 2017

    Full-Spectrum Solar-Light-Activated Photocatalysts for Light-Chemical Energy Conversion
    journal, June 2017

    • Wang, Xiaoning; Wang, Fulei; Sang, Yuanhua
    • Advanced Energy Materials, Vol. 7, Issue 23
    • DOI: 10.1002/aenm.201700473

    Mechanistic Studies of Plasmon Chemistry on Metal Catalysts
    journal, February 2019

    • Kazuma, Emiko; Kim, Yousoo
    • Angewandte Chemie International Edition, Vol. 58, Issue 15
    • DOI: 10.1002/anie.201811234

    Reaction Pathway Dependence in Plasmonic Catalysis: Hydrogenation as a Model Molecular Transformation
    journal, February 2018

    • Barbosa, Eduardo C. M.; Fiorio, Jhonatan L.; Mou, Tong
    • Chemistry - A European Journal, Vol. 24, Issue 47
    • DOI: 10.1002/chem.201705749

    A surfactant‐free synthesis of the silica nanosphere‐supported ultrafine silver nanoparticles and their antibacterial effects
    journal, April 2019

    • Shen, Qihui; Shan, Yixuan; Lü, Yang
    • Journal of the Chinese Chemical Society, Vol. 66, Issue 8
    • DOI: 10.1002/jccs.201900105

    Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis
    journal, February 2018

    Utilization of hybrid plasmonic modes to investigate surface interactions between nanocubes and polymer substrates
    journal, February 2017

    Plasmonic hot electron transfer-induced multicolor MoO3-x-based chromogenic system for visual and colorimetric determination of silver(I)
    journal, January 2020

    Product selectivity in plasmonic photocatalysis for carbon dioxide hydrogenation
    journal, February 2017

    • Zhang, Xiao; Li, Xueqian; Zhang, Du
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14542

    Plasmonic photoluminescence for recovering native chemical information from surface-enhanced Raman scattering
    journal, March 2017

    • Lin, Kai-Qiang; Yi, Jun; Zhong, Jin-Hui
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14891

    Controlling energy flow in multimetallic nanostructures for plasmonic catalysis
    journal, July 2017

    • Aslam, Umar; Chavez, Steven; Linic, Suljo
    • Nature Nanotechnology, Vol. 12, Issue 10
    • DOI: 10.1038/nnano.2017.131

    Site-selective CO disproportionation mediated by localized surface plasmon resonance excited by electron beam
    journal, April 2019

    Plasmonic coupling at a metal/semiconductor interface
    journal, November 2017

    Catalytic conversion of solar to chemical energy on plasmonic metal nanostructures
    journal, September 2018

    Plasmon-induced charge separation: chemistry and wide applications
    journal, January 2017

    • Tatsuma, Tetsu; Nishi, Hiroyasu; Ishida, Takuya
    • Chemical Science, Vol. 8, Issue 5
    • DOI: 10.1039/c7sc00031f

    Using plasmonically generated carriers as redox equivalents
    journal, January 2020

    • Yu, Sungju; Mohan, Varun; Jain, Prashant K.
    • MRS Bulletin, Vol. 45, Issue 1
    • DOI: 10.1557/mrs.2019.293
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