Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Vinogradov, Ilya; Singh, Suryansh; Lyle, Hanna; Paolino, Michael; Mandal, Aritra; Rossmeisl, Jan; Cuk, Tanja

doi:10.1038/s41563-021-01118-9

Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Journal Article · Mon Nov 01 00:00:00 EDT 2021 · Nature Materials

DOI:https://doi.org/10.1038/s41563-021-01118-9· OSTI ID:1831508

^[1]; Singh, Suryansh ^[2]; Lyle, Hanna ^[2]; Paolino, Michael ^[2]; ^[2]; ^[3]; ^[2]

Univ. of Colorado, Boulder, CO (United States); University of Colorado, Boulder
Univ. of Colorado, Boulder, CO (United States)
Univ. of Copenhagen (Denmark)

Theoretical descriptors differentiate the catalytic activity of materials for the oxygen evolution reaction by the strength of oxygen binding in the reactive intermediate created upon electron transfer. Recently, time-resolved spectroscopy of a photo-electrochemically driven oxygen evolution reaction followed the vibrational and optical spectra of this intermediate, denoted M-OH*. However, these inherently kinetic experiments have not been connected to the relevant thermodynamic quantities. Here we discover that picosecond optical spectra of the Ti-OH* population on lightly doped SrTiO₃ are ordered by the surface hydroxylation. A Langmuir isotherm as a function of pH extracts an effective equilibrium constant relatable to the free energy difference of the first oxygen evolution reaction step. Thus, time-resolved spectroscopy of the catalytic surface reveals both kinetic and energetic information of elementary reaction steps, which provides a critical new connection between theory and experiment by which to tailor the pathway of water oxidation and other surface reactions.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018939

OSTI ID:: 1831508

Journal Information:: Nature Materials, Journal Name: Nature Materials Vol. 21; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Sustainable Nanoplasmon‐Enhanced Photoredox Reactions: Synthesis, Characterization, and Applications Bhattacharya, Chirasmita; Saji, Sandra Elizabeth; Mohan, Akhil Advanced Energy Materials, Vol. 10, Issue 40 https://doi.org/10.1002/aenm.202002402	journal	September 2020
Chemical Imaging of Spatial Heterogeneities in Catalytic Solids at Different Length and Time Scales Weckhuysen, Bert M. Angewandte Chemie International Edition, Vol. 48, Issue 27 https://doi.org/10.1002/anie.200900339	journal	June 2009
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201000397	journal	March 2011
Towards a Molecular Level Understanding of the Multi-Electron Catalysis of Water Oxidation on Metal Oxide Surfaces Zhang, Miao; Frei, Heinz Catalysis Letters, Vol. 145, Issue 1 https://doi.org/10.1007/s10562-014-1437-8	journal	November 2014
Impact of cleaning methods on the structural properties and morphology of SrTiO3 surface Arnay, Iciar; Rubio-Zuazo, Juan; Castro, German R. Applied Surface Science, Vol. 427 https://doi.org/10.1016/j.apsusc.2017.09.025	journal	January 2018
Electrolysis of water on oxide surfaces Rossmeisl, J.; Qu, Z. -W.; Zhu, H. Journal of Electroanalytical Chemistry, Vol. 607, Issue 1-2 https://doi.org/10.1016/j.jelechem.2006.11.008	journal	September 2007
Beyond the top of the volcano? – A unified approach to electrocatalytic oxygen reduction and oxygen evolution Busch, Michael; Halck, Niels B.; Kramm, Ulrike I. Nano Energy, Vol. 29 https://doi.org/10.1016/j.nanoen.2016.04.011	journal	November 2016
A review on thermalization mechanisms and prospect absorber materials for the hot carrier solar cells Zhang, Yi; Jia, Xuguang; Liu, Shuang Solar Energy Materials and Solar Cells, Vol. 225 https://doi.org/10.1016/j.solmat.2021.111073	journal	June 2021
Surface-Sensitive and Surface-Specific Ultrafast Two-Dimensional Vibrational Spectroscopy Kraack, Jan Philip; Hamm, Peter Chemical Reviews, Vol. 117, Issue 16 https://doi.org/10.1021/acs.chemrev.6b00437	journal	December 2016
Surface Enhancement in Ultrafast 2D ATR IR Spectroscopy at the Metal-Liquid Interface Kraack, Jan Philip; Kaech, Andres; Hamm, Peter The Journal of Physical Chemistry C, Vol. 120, Issue 6 https://doi.org/10.1021/acs.jpcc.5b11051	journal	February 2016
Differences in the Vibrational Dynamics of H ₂ O and D ₂ O: Observation of Symmetric and Antisymmetric Stretching Vibrations in Heavy Water De Marco, Luigi; Carpenter, William; Liu, Hanchao The Journal of Physical Chemistry Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acs.jpclett.6b00668	journal	April 2016
Langmuir’s Theory of Adsorption: A Centennial Review Swenson, Hans; Stadie, Nicholas P. Langmuir, Vol. 35, Issue 16 https://doi.org/10.1021/acs.langmuir.9b00154	journal	March 2019
Water Oxidation Kinetics of Accumulated Holes on the Surface of a TiO ₂ Photoanode: A Rate Law Analysis Kafizas, Andreas; Ma, Yimeng; Pastor, Ernest ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b01150	journal	June 2017
Aqueous Basic Solutions: Hydroxide Solvation, Structural Diffusion, and Comparison to the Hydrated Proton Marx, Dominik; Chandra, Amalendu; Tuckerman, Mark E. Chemical Reviews, Vol. 110, Issue 4 https://doi.org/10.1021/cr900233f	journal	April 2010
Acidity of the Aqueous Rutile TiO ₂ (110) Surface from Density Functional Theory Based Molecular Dynamics Cheng, Jun; Sprik, Michiel Journal of Chemical Theory and Computation, Vol. 6, Issue 3 https://doi.org/10.1021/ct100013q	journal	February 2010
Photoelectrochemical and Impedance Spectroscopic Investigation of Water Oxidation with “Co–Pi”-Coated Hematite Electrodes Klahr, Benjamin; Gimenez, Sixto; Fabregat-Santiago, Francisco Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja306427f	journal	September 2012
Chemical Dynamics of the First Proton-Coupled Electron Transfer of Water Oxidation on TiO ₂ Anatase Chen, Jia; Li, Ye-Fei; Sit, Patrick Journal of the American Chemical Society, Vol. 135, Issue 50 https://doi.org/10.1021/ja410685m	journal	December 2013
How Surface Potential Determines the Kinetics of the First Hole Transfer of Photocatalytic Water Oxidation Waegele, Matthias M.; Chen, Xihan; Herlihy, David M. Journal of the American Chemical Society, Vol. 136, Issue 30 https://doi.org/10.1021/ja503603k	journal	July 2014
Rate Law Analysis of Water Oxidation on a Hematite Surface Le Formal, Florian; Pastor, Ernest; Tilley, S. David Journal of the American Chemical Society, Vol. 137, Issue 20 https://doi.org/10.1021/jacs.5b02576	journal	May 2015
The Formation Time of Ti–O ^• and Ti–O ^• –Ti Radicals at the n-SrTiO ₃ /Aqueous Interface during Photocatalytic Water Oxidation Chen, Xihan; Choing, Stephanie N.; Aschaffenburg, Daniel J. Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.6b09550	journal	December 2016
Proton Transfer in Concentrated Aqueous Hydroxide Visualized Using Ultrafast Infrared Spectroscopy Roberts, Sean T.; Ramasesha, Krupa; Petersen, Poul B. The Journal of Physical Chemistry A, Vol. 115, Issue 16 https://doi.org/10.1021/jp108474p	journal	April 2011
Identifying Trapped Electronic Holes at the Aqueous TiO ₂ Interface Cheng, Jun; VandeVondele, Joost; Sprik, Michiel The Journal of Physical Chemistry C, Vol. 118, Issue 10 https://doi.org/10.1021/jp500769q	journal	March 2014
Intrinsic Hole Migration Rates in TiO ₂ from Density Functional Theory Deskins, N. Aaron; Dupuis, Michel The Journal of Physical Chemistry C, Vol. 113, Issue 1 https://doi.org/10.1021/jp802903c	journal	December 2008
Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy Buurmans, Inge L. C.; Weckhuysen, Bert M. Nature Chemistry, Vol. 4, Issue 11 https://doi.org/10.1038/nchem.1478	journal	October 2012
Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst Zhang, Miao; de Respinis, Moreno; Frei, Heinz Nature Chemistry, Vol. 6, Issue 4 https://doi.org/10.1038/nchem.1874	journal	February 2014
Detecting the oxyl radical of photocatalytic water oxidation at an n-SrTiO3/aqueous interface through its subsurface vibration Herlihy, David M.; Waegele, Matthias M.; Chen, Xihan Nature Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/nchem.2497	journal	April 2016
Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy Zandi, Omid; Hamann, Thomas W. Nature Chemistry, Vol. 8, Issue 8 https://doi.org/10.1038/nchem.2557	journal	July 2016
Interfacing electrochemistry Markovic, Nenad M. Nature Materials, Vol. 12, Issue 2 https://doi.org/10.1038/nmat3554	journal	January 2013
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces Selcuk, Sencer; Selloni, Annabella Nature Materials, Vol. 15, Issue 10 https://doi.org/10.1038/nmat4672	journal	June 2016
Structures of the intermediates of Kok’s photosynthetic water oxidation clock Kern, Jan; Chatterjee, Ruchira; Young, Iris D. Nature, Vol. 563, Issue 7731 https://doi.org/10.1038/s41586-018-0681-2	journal	November 2018
Selecting between two transition states by which water oxidation intermediates decay on an oxide surface Chen, Xihan; Aschaffenburg, Daniel J.; Cuk, Tanja Nature Catalysis, Vol. 2, Issue 9 https://doi.org/10.1038/s41929-019-0332-5	journal	August 2019
The nature of the active site in heterogeneous metal catalysis Nørskov, Jens K.; Bligaard, Thomas; Hvolbæk, Britt Chemical Society Reviews, Vol. 37, Issue 10 https://doi.org/10.1039/b800260f	journal	January 2008
Coherent two-dimensional infrared spectroscopy: Quantitative analysis of protein secondary structure in solution Baiz, Carlos R.; Peng, Chunte Sam; Reppert, Mike E. The Analyst, Vol. 137, Issue 8 https://doi.org/10.1039/c2an16031e	journal	January 2012
The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen Parsons, Roger Transactions of the Faraday Society, Vol. 54, p. 1053-1063 https://doi.org/10.1039/tf9585401053	journal	January 1958
A molecular beam/surface spectroscopy apparatus for the study of reactions on complex model catalysts Libuda, J.; Meusel, I.; Hartmann, J. Review of Scientific Instruments, Vol. 71, Issue 12 https://doi.org/10.1063/1.1318919	journal	January 2000
Blue luminescence of SrTiO3 under intense optical excitation Rubano, A.; Paparo, D.; Granozio, F. Miletto Journal of Applied Physics, Vol. 106, Issue 10 https://doi.org/10.1063/1.3256140	journal	November 2009
Two-dimensional infrared spectroscopy of isotope-diluted ice Ih Perakis, Fivos; Widmer, Susanne; Hamm, Peter The Journal of Chemical Physics, Vol. 134, Issue 20 https://doi.org/10.1063/1.3592561	journal	May 2011
Collective vibrations of water-solvated hydroxide ions investigated with broadband 2DIR spectroscopy Mandal, Aritra; Ramasesha, Krupa; De Marco, Luigi The Journal of Chemical Physics, Vol. 140, Issue 20 https://doi.org/10.1063/1.4878490	journal	May 2014
A first-principles study of H ₂ O adsorption and dissociation on the SrTiO ₃ (100) surface Hinojosa, Beverly Brooks; Van Cleve, Tim; Asthagiri, Aravind Molecular Simulation, Vol. 36, Issue 7-8 https://doi.org/10.1080/08927021003762746	journal	June 2010
Photoluminescence and reversible photo-induced spectral change of SrTiO ₃ Mochizuki, Shosuke; Fujishiro, Fumito; Minami, Seiko Journal of Physics: Condensed Matter, Vol. 17, Issue 6 https://doi.org/10.1088/0953-8984/17/6/011	journal	January 2005
O ⁻ bound small polarons in oxide materials Schirmer, O. F. Journal of Physics: Condensed Matter, Vol. 18, Issue 43 https://doi.org/10.1088/0953-8984/18/43/R01	journal	October 2006
The interface of SrTiO ₃ and H ₂ O from density functional theory molecular dynamics Holmström, E.; Spijker, P.; Foster, A. S. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 472, Issue 2193 https://doi.org/10.1098/rspa.2016.0293	journal	September 2016
Water adsorption and dissociation on SrTiO 3 ( 001 ) revisited: A density functional theory study Guhl, Hannes; Miller, Wolfram; Reuter, Karsten Physical Review B, Vol. 81, Issue 15 https://doi.org/10.1103/PhysRevB.81.155455	journal	April 2010
Hole localization, migration, and the formation of peroxide anion in perovskite Sr Ti O 3 Chen, Hungru; Umezawa, Naoto Physical Review B, Vol. 90, Issue 3 https://doi.org/10.1103/PhysRevB.90.035202	journal	July 2014
Vacancies and small polarons in SrTiO 3 Janotti, Anderson; Varley, Joel B.; Choi, Minseok Physical Review B, Vol. 90, Issue 8 https://doi.org/10.1103/PhysRevB.90.085202	journal	August 2014
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017
On the Early History of the Singular Value Decomposition Stewart, G. W. SIAM Review, Vol. 35, Issue 4 https://doi.org/10.1137/1035134	journal	December 1993
Assessment of Polishing-Related Surface Damage in Silicon Carbide Sanchez, E. K.; Ha, S.; Grim, J. Journal of The Electrochemical Society, Vol. 149, Issue 2 https://doi.org/10.1149/1.1430416	journal	January 2002
General noise suppression scheme with reference detection in heterodyne nonlinear spectroscopy Feng, Yuan; Vinogradov, Ilya; Ge, Nien-Hui Optics Express, Vol. 25, Issue 21 https://doi.org/10.1364/OE.25.026262	journal	January 2017
Optimized noise reduction scheme for heterodyne spectroscopy using array detectors Feng, Yuan; Vinogradov, Ilya; Ge, Nien-Hui Optics Express, Vol. 27, Issue 15 https://doi.org/10.1364/OE.27.020323	journal	January 2019
The absolute energy positions of conduction and valence bands of selected semiconducting minerals Xu, Yong; Schoonen, Martin A. A. American Mineralogist, Vol. 85, Issue 3-4 https://doi.org/10.2138/am-2000-0416	journal	March 2000

Similar Records

Coherent Acoustic Interferometry during the Photodriven Oxygen Evolution Reaction Associates Strain Fields with the Reactive Oxygen Intermediate (Ti–OH*)

Journal Article · Wed Sep 22 20:00:00 EDT 2021 · Journal of the American Chemical Society · OSTI ID:1831511

The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy

Journal Article · Wed Aug 18 20:00:00 EDT 2021 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1831510

Phenomenology of Intermediate Molecular Dynamics at Metal-Oxide Interfaces

Journal Article · Thu Jun 27 20:00:00 EDT 2024 · Annual Review of Physical Chemistry · OSTI ID:2580100

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Citation Formats

References (51)

Similar Records

Related Subjects