In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode
Abstract
Illumination of a voltage-biased plasmonic Ag cathode during CO2 reduction results in a suppression of the H2 evolution reaction while enhancing CO2 reduction. This effect has been shown to be photonic rather than thermal, but the exact plasmonic mechanism is unknown. Here in this paper, we conduct an in situ ATR–SEIRAS (attenuated total reflectance–surface-enhanced infrared absorption spectroscopy) study of a sputtered thin film Ag cathode on a Ge ATR crystal in CO2-saturated 0.1 M KHCO3 over a range of potentials under both dark and illuminated (365 nm, 125 mW cm–2) conditions to elucidate the nature of this plasmonic enhancement. We find that the onset potential of CO2 reduction to adsorbed CO on the Ag surface is -0.25 VRHE and is identical in the light and the dark. As the production of gaseous CO is detected in the light near this onset potential but is not observed in the dark until -0.5 VRHE, we conclude that the light must be assisting the desorption of CO from the surface. Furthermore, the HCO3– wavenumber and peak area increase immediately upon illumination, precluding a thermal effect. We propose that the enhanced local electric field that results from the localized surface plasmon resonance (LSPR) ismore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Delft Univ. of Technology (Netherlands)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Delft Univ. of Technology (Netherlands); National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Dutch Research Council
- OSTI Identifier:
- 1660043
- Alternate Identifier(s):
- OSTI ID: 1631677
- Report Number(s):
- NREL/JA-5900-77272
Journal ID: ISSN 0002-7863; MainId:26218;UUID:943af55c-0d67-4fbd-a46f-0c16c7fcbb8e;MainAdminID:13811
- Grant/Contract Number:
- AC36-08GO28308; CBET-1653430; SC0004993; DGE 1106400; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 27; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ATR-SEIRAS; attenuated total reflectance-surface-enhanced infrared absorption spectroscopy; electrochemical structure; thin film
Citation Formats
Corson, Elizabeth R., Kas, Recep, Kostecki, Robert, Urban, Jeffrey J., Smith, Wilson A., McCloskey, Bryan D., and Kortlever, Ruud. In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c01953.
Corson, Elizabeth R., Kas, Recep, Kostecki, Robert, Urban, Jeffrey J., Smith, Wilson A., McCloskey, Bryan D., & Kortlever, Ruud. In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode. United States. https://doi.org/10.1021/jacs.0c01953
Corson, Elizabeth R., Kas, Recep, Kostecki, Robert, Urban, Jeffrey J., Smith, Wilson A., McCloskey, Bryan D., and Kortlever, Ruud. Fri .
"In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode". United States. https://doi.org/10.1021/jacs.0c01953. https://www.osti.gov/servlets/purl/1660043.
@article{osti_1660043,
title = {In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode},
author = {Corson, Elizabeth R. and Kas, Recep and Kostecki, Robert and Urban, Jeffrey J. and Smith, Wilson A. and McCloskey, Bryan D. and Kortlever, Ruud},
abstractNote = {Illumination of a voltage-biased plasmonic Ag cathode during CO2 reduction results in a suppression of the H2 evolution reaction while enhancing CO2 reduction. This effect has been shown to be photonic rather than thermal, but the exact plasmonic mechanism is unknown. Here in this paper, we conduct an in situ ATR–SEIRAS (attenuated total reflectance–surface-enhanced infrared absorption spectroscopy) study of a sputtered thin film Ag cathode on a Ge ATR crystal in CO2-saturated 0.1 M KHCO3 over a range of potentials under both dark and illuminated (365 nm, 125 mW cm–2) conditions to elucidate the nature of this plasmonic enhancement. We find that the onset potential of CO2 reduction to adsorbed CO on the Ag surface is -0.25 VRHE and is identical in the light and the dark. As the production of gaseous CO is detected in the light near this onset potential but is not observed in the dark until -0.5 VRHE, we conclude that the light must be assisting the desorption of CO from the surface. Furthermore, the HCO3– wavenumber and peak area increase immediately upon illumination, precluding a thermal effect. We propose that the enhanced local electric field that results from the localized surface plasmon resonance (LSPR) is strengthening the HCO3– bond, further increasing the local pH. This would account for the decrease in H2 formation and increase the CO2 reduction products in the light.},
doi = {10.1021/jacs.0c01953},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 142,
place = {United States},
year = {Fri May 29 00:00:00 EDT 2020},
month = {Fri May 29 00:00:00 EDT 2020}
}
Web of Science
Works referenced in this record:
Molecular Orbital View of Chemisorbed Carbon Monoxide
journal, October 1964
- Blyholder, George
- The Journal of Physical Chemistry, Vol. 68, Issue 10
In Situ Infrared Spectroscopy Reveals Persistent Alkalinity near Electrode Surfaces during CO 2 Electroreduction
journal, September 2019
- Yang, Kailun; Kas, Recep; Smith, Wilson A.
- Journal of the American Chemical Society, Vol. 141, Issue 40
What would it take for renewably powered electrosynthesis to displace petrochemical processes?
journal, April 2019
- De Luna, Phil; Hahn, Christopher; Higgins, Drew
- Science, Vol. 364, Issue 6438
Surface-Plasmon-Assisted Photoelectrochemical Reduction of CO 2 and NO 3 − on Nanostructured Silver Electrodes
journal, May 2018
- Kim, Youngsang; Creel, Erin B.; Corson, Elizabeth R.
- Advanced Energy Materials, Vol. 8, Issue 22
Directing Selectivity of Electrochemical Carbon Dioxide Reduction Using Plasmonics
journal, April 2019
- Creel, Erin B.; Corson, Elizabeth R.; Eichhorn, Johanna
- ACS Energy Letters, Vol. 4, Issue 5
Platinum electrocatalysts with plasmonic nano-cores for photo-enhanced oxygen-reduction
journal, November 2017
- Zheng, Zhaoke; Xie, Wen; Li, Mengmeng
- Nano Energy, Vol. 41
Plasmonic-Enhanced Oxygen Reduction Reaction of Silver/Graphene Electrocatalysts
journal, January 2019
- Shi, Fenglei; He, Jing; Zhang, Baiyu
- Nano Letters, Vol. 19, Issue 2
Boosting electrocatalytic hydrogen evolution by plasmon-driven hot-electron excitation
journal, January 2018
- Zhang, Hai-Xia; Li, Yang; Li, Min-Yu
- Nanoscale, Vol. 10, Issue 5
Plasmon-enhanced electrocatalytic hydrogen/oxygen evolution by Pt/Fe–Au nanorods
journal, January 2018
- Guo, Xia; Li, Xiaotong; Kou, Shufang
- Journal of Materials Chemistry A, Vol. 6, Issue 17
Mechanistic Understanding of Plasmon-Enhanced Electrochemistry
journal, November 2019
- Wilson, Andrew J.; Mohan, Varun; Jain, Prashant K.
- The Journal of Physical Chemistry C, Vol. 123, Issue 48
Insights into the electrocatalytic reduction of CO 2 on metallic silver surfaces
journal, January 2014
- Hatsukade, Toru; Kuhl, Kendra P.; Cave, Etosha R.
- Phys. Chem. Chem. Phys., Vol. 16, Issue 27
Carbon Monoxide Adsorption on Copper and Silver Electrodes during Carbon Dioxide Electroreduction Studied by Infrared Reflection Absorption Spectroscopy and Surface-Enhanced Raman Spectroscopy
journal, January 1996
- Oda, Ichiro; Ogasawara, Hirohito; Ito, Masatoki
- Langmuir, Vol. 12, Issue 4, p. 1094-1097
Probing the Reaction Mechanism of CO 2 Electroreduction over Ag Films via Operando Infrared Spectroscopy
journal, December 2016
- Firet, Nienke J.; Smith, Wilson A.
- ACS Catalysis, Vol. 7, Issue 1
Examination of Near-Electrode Concentration Gradients and Kinetic Impacts on the Electrochemical Reduction of CO 2 using Surface-Enhanced Infrared Spectroscopy
journal, April 2018
- Dunwell, Marco; Yang, Xuan; Setzler, Brian P.
- ACS Catalysis, Vol. 8, Issue 5
A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper
journal, August 2006
- Gattrell, M.; Gupta, N.; Co, A.
- Journal of Electroanalytical Chemistry, Vol. 594, Issue 1, p. 1-19
Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO 2 Reduction
journal, May 2017
- Gunathunge, Charuni M.; Li, Xiang; Li, Jingyi
- The Journal of Physical Chemistry C, Vol. 121, Issue 22
In Situ Infrared Spectroscopy Reveals Persistent Alkalinity near Electrode Surfaces during CO 2 Electroreduction
journal, September 2019
- Yang, Kailun; Kas, Recep; Smith, Wilson A.
- Journal of the American Chemical Society, Vol. 141, Issue 40
In‐Situ Infrared Spectroscopy Applied to the Study of the Electrocatalytic Reduction of CO 2 : Theory, Practice and Challenges
journal, September 2019
- Kas, Recep; Ayemoba, Onagie; Firet, Nienke J.
- ChemPhysChem, Vol. 20, Issue 22
In Situ IR Observation of Surface Species during the Photocatalytic Decomposition of Acetic Acid over TiO 2 Films
journal, September 2002
- Sato, Shinri; Ueda, Kazuhiro; Kawasaki, Yasuhiro
- The Journal of Physical Chemistry B, Vol. 106, Issue 35
Primary Intermediates of Oxygen Photoevolution Reaction on TiO 2 (Rutile) Particles, Revealed by in Situ FTIR Absorption and Photoluminescence Measurements
journal, February 2004
- Nakamura, Ryuhei; Nakato, Yoshihiro
- Journal of the American Chemical Society, Vol. 126, Issue 4
Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy
journal, July 2016
- Zandi, Omid; Hamann, Thomas W.
- Nature Chemistry, Vol. 8, Issue 8
In Situ Infrared Spectroscopy of Glyoxylic Acid Adsorption and Photocatalysis on TiO 2 in Aqueous Solution
journal, December 1999
- Ekström, G. Niklas; McQuillan, A. James
- The Journal of Physical Chemistry B, Vol. 103, Issue 48
A temperature-controlled photoelectrochemical cell for quantitative product analysis
journal, May 2018
- Corson, Elizabeth R.; Creel, Erin B.; Kim, Youngsang
- Review of Scientific Instruments, Vol. 89, Issue 5
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012
- Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
- Energy & Environmental Science, Vol. 5, Issue 5
Silver island films for surface-enhanced infrared absorption spectroscopy: effect of island morphology on the absorption enhancement
journal, October 1993
- Nishikawa, Yuji; Nagasawa, Tadahiro; Fujiwara, Kunihiro
- Vibrational Spectroscopy, Vol. 6, Issue 1
A comparison between chemical and sputtering methods for preparing thin-film silver electrodes for in situ ATR-SEIRAS studies
journal, April 2007
- Delgado, José Manuel; Orts, José Manuel; Rodes, Antonio
- Electrochimica Acta, Vol. 52, Issue 14
Synthesis and TEM study of nanoparticles and nanocrystalline thin films of silver by high pressure sputtering
journal, November 1999
- Chandra, Ramesh; Taneja, Praveen; John, J.
- Nanostructured Materials, Vol. 11, Issue 8
Growth and morphology of magnetron sputter deposited silver films
journal, March 2002
- Del Re, M.; Gouttebaron, R.; Dauchot, J. P.
- Surface and Coatings Technology, Vol. 151-152
Fourier-transform infrared, attenuated total reflection spectroscopy: a complementary tool for the investigation of the adsorption of CO on thin metal layers
journal, January 1991
- Zippel, Erich; Breiter, Manfred W.; Kellner, Robert
- Journal of the Chemical Society, Faraday Transactions, Vol. 87, Issue 4
Voltage-dependent ordering of water molecules at an electrode–electrolyte interface
journal, March 1994
- Toney, Michael F.; Howard, Jason N.; Richer, Jocelyn
- Nature, Vol. 368, Issue 6470
Potential Dependent Organization of Water at the Electrified Metal−Liquid Interface
journal, November 2005
- Schultz, Zachary D.; Shaw, Scott K.; Gewirth, Andrew A.
- Journal of the American Chemical Society, Vol. 127, Issue 45
In Situ Infrared Study of Water−Sulfate Coadsorption on Gold(111) in Sulfuric Acid Solutions
journal, February 1998
- Ataka, Ken-ichi; Osawa, Masatoshi
- Langmuir, Vol. 14, Issue 4
In situ infrared spectroscopy at electrochemical interfaces
journal, August 1997
- Iwasita, T.; Nart, F. C.
- Progress in Surface Science, Vol. 55, Issue 4
Comparative study of CO adsorbed on Pt, Pd, Au and Ag electrodes in neutral solution by IR reflection absorption spectroscopy
journal, October 1988
- Ikezawa, Yasunari; Saito, Hiroshi; Matsubayashi, Hideyuki
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 252, Issue 2
In-situ infrared spectroscopy of the electrode/electrolyte solution interphase
journal, July 1983
- Bewick, A.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2
Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces
journal, January 2017
- Dunwell, M.; Wang, Junhua; Yan, Y.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 2
Potential Routes and Mitigation Strategies for Contamination in Interfacial Specific Infrared Spectroelectrochemical Studies
journal, September 2018
- Dunwell, Marco; Yang, Xuan; Yan, Yushan
- The Journal of Physical Chemistry C, Vol. 122, Issue 43
Field-dependent chemisorption of carbon monoxide and nitric oxide on platinum-group (111) surfaces: Quantum chemical calculations compared with infrared spectroscopy at electrochemical and vacuum-based interfaces
journal, September 2000
- Koper, Marc T. M.; van Santen, Rutger A.; Wasileski, Sally A.
- The Journal of Chemical Physics, Vol. 113, Issue 10
Molecular Orbital View of Chemisorbed Carbon Monoxide
journal, October 1964
- Blyholder, George
- The Journal of Physical Chemistry, Vol. 68, Issue 10
Electromagnetic mechanism of enhanced infrared absorption of molecules adsorbed on metal island films
journal, February 1992
- Osawa, Masatoshi; Ataka, Ken-ichi
- Surface Science, Vol. 262, Issue 3
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
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014
- Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
- Journal of the American Chemical Society, Vol. 136, Issue 40
Reaction Selectivity for Plasmon-Driven Carbon Dioxide Reduction on Silver Clusters: A Theoretical Prediction
journal, February 2019
- Zhang, Xia-Guang; Liu, Yuxiu; Zhan, Chao
- The Journal of Physical Chemistry C, Vol. 123, Issue 17
Surface Plasmon-Mediated Photothermal Chemistry
journal, July 2014
- Qiu, Jingjing; Wei, Wei David
- The Journal of Physical Chemistry C, Vol. 118, Issue 36
Formation of subsurface oxygen species and its high activity toward CO oxidation over silver catalysts
journal, January 2005
- Qu, Z.; Cheng, M.; Huang, W.
- Journal of Catalysis, Vol. 229, Issue 2
Photochemical transformations on plasmonic metal nanoparticles
journal, May 2015
- Linic, Suljo; Aslam, Umar; Boerigter, Calvin
- Nature Materials, Vol. 14, Issue 6
Desorption induced by femtosecond laser pulses
journal, March 1990
- Prybyla, J. A.; Heinz, T. F.; Misewich, J. A.
- Physical Review Letters, Vol. 64, Issue 13
Femtosecond time-resolved surface reaction: Desorption of Co from Cu(111) in <325 fsec
journal, January 1992
- Prybyla, J. A.; Tom, H. W. K.; Aumiller, G. D.
- Physical Review Letters, Vol. 68, Issue 4
Dynamics of Electron-Induced Manipulation of Individual CO Molecules on Cu(111)
journal, March 1998
- Bartels, L.; Meyer, G.; Rieder, K. -H.
- Physical Review Letters, Vol. 80, Issue 9
Electronic Excitation and Dynamic Promotion of a Surface Reaction
journal, November 2003
- Denzler, D. N.; Frischkorn, C.; Hess, C.
- Physical Review Letters, Vol. 91, Issue 22
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
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
Plasmon-induced selective carbon dioxide conversion on earth-abundant aluminum-cuprous oxide antenna-reactor nanoparticles
journal, June 2017
- Robatjazi, Hossein; Zhao, Hangqi; Swearer, Dayne F.
- Nature Communications, Vol. 8, Issue 1
In-situ infrared spectroscopy of water and electrolytes adsorbed on a Pt(111) electrode surface in acid solution. Structural changes of adsorbed water molecules upon an electrode potential
journal, March 1996
- Hirota, Koji; Song, Moon-Bong; Ito, Masatoki
- Chemical Physics Letters, Vol. 250, Issue 3-4
A surface-enhanced infrared absorption spectroscopic study of pH dependent water adsorption on Au
journal, August 2016
- Dunwell, Marco; Yan, Yushan; Xu, Bingjun
- Surface Science, Vol. 650
Potential-Dependent Reorientation of Water Molecules at an Electrode/Electrolyte Interface Studied by Surface-Enhanced Infrared Absorption Spectroscopy
journal, January 1996
- Ataka, Ken-ichi; Yotsuyanagi, Takao; Osawa, Masatoshi
- The Journal of Physical Chemistry, Vol. 100, Issue 25
A new structure of water layer on Cu(111) electrode surface during hydrogen evolution
journal, January 2006
- Ito, Masatoki; Yamazaki, Mizuho
- Physical Chemistry Chemical Physics, Vol. 8, Issue 31
A vibrational-spectroscopic study of the species present in the CO2?H2O system
journal, October 1972
- Davis, A. R.; Oliver, B. G.
- Journal of Solution Chemistry, Vol. 1, Issue 4
Vibrational Spectroscopic Studies of Aqueous Alkali Metal Bicarbonate and Carbonate Solutions
journal, March 1973
- Oliver, Barry G.; Davis, Anthony R.
- Canadian Journal of Chemistry, Vol. 51, Issue 5
Vibrational Spectroscopic Studies and Density Functional Theory Calculations of Speciation in the CO 2 —Water System
journal, February 2006
- Rudolph, Wolfram W.; Fischer, Dieter; Irmer, Gert
- Applied Spectroscopy, Vol. 60, Issue 2
Magnesium bicarbonate and carbonate interactions in aqueous solutions: An infrared spectroscopic and quantum chemical study
journal, February 2017
- Stefánsson, Andri; Lemke, Kono H.; Bénézeth, Pascale
- Geochimica et Cosmochimica Acta, Vol. 198
Infrared Spectroscopy of Hydrated Bicarbonate Anion Clusters: HCO 3 − (H 2 O) 1−10
journal, January 2010
- Garand, Etienne; Wende, Torsten; Goebbert, Daniel J.
- Journal of the American Chemical Society, Vol. 132, Issue 2
Structure and Vibrational Spectrum of Formate and Acetate Adsorbed from Aqueous Solution onto the TiO 2 Rutile (110) Surface
journal, April 2004
- Rotzinger, François P.; Kesselman-Truttmann, Janet M.; Hug, Stephan J.
- The Journal of Physical Chemistry B, Vol. 108, Issue 16
Spectroscopic Evidence of Size-Dependent Buffering of Interfacial pH by Cation Hydrolysis during CO 2 Electroreduction
journal, August 2017
- Ayemoba, Onagie; Cuesta, Angel
- ACS Applied Materials & Interfaces, Vol. 9, Issue 33
Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide
journal, January 2015
- Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 29
A HREELS study of C1C5 straight chain alcohols on clean and pre-oxidized Ag(110) surfaces
journal, November 1991
- Dai, Qing; Gellman, Andrew J.
- Surface Science, Vol. 257, Issue 1-3
Influence of dilute feed and pH on electrochemical reduction of CO2 to CO on Ag in a continuous flow electrolyzer
journal, June 2015
- Kim, Byoungsu; Ma, Sichao; Molly Jhong, Huei-Ru
- Electrochimica Acta, Vol. 166, p. 271-276
Quantitative Detection of Photothermal and Photoelectrocatalytic Effects Induced by SPR from Au@Pt Nanoparticles
journal, August 2015
- Yang, Hao; He, Lan-Qi; Hu, Yu-Wen
- Angewandte Chemie International Edition, Vol. 54, Issue 39