Combining Experiment and Theory To Unravel the Mechanism of Two-Electron Oxygen Reduction at a Selective and Active Co-catalyst

Bukas, Vanessa J.; Kim, Hyo Won; Sengpiel, Robert; Knudsen, Kristian; Voss, Johannes; McCloskey, Bryan D.; Luntz, Alan C.

doi:10.1021/acscatal.8b02813

Title: Combining Experiment and Theory To Unravel the Mechanism of Two-Electron Oxygen Reduction at a Selective and Active Co-catalyst

Journal Article · 08 November 2018 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.8b02813 · OSTI ID:1493410

^[1]; Kim, Hyo Won ^[2]; Sengpiel, Robert ^[2]; Knudsen, Kristian ^[2];

^[1];

^[3];

^[1]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

In this work, we present a combination of comprehensive experimental and theoretical evidence to unravel the mechanism of two-electron oxygen reduction reaction (ORR) on a catalyst composed of mildly reduced graphene oxide supported on P50 carbon paper (mrGO/P50). This catalyst is unique in that it shows >99% selectivity toward H₂O₂, the highest mass activity to date, and essentially zero overpotential in base. Furthermore, the mrGO catalytically active site is unambiguously identified and presents a unique opportunity to investigate mechanisms of carbon-based catalysis in atomistic detail. A wide range of experiments at varying pH are reported: ORR onset potential, Tafel slopes, H/D kinetic isotope effects, and O₂ reaction order. With DFT reaction energies and known thermodynamic parameters, we calculate the potential and pH-dependent free energies of all possible intermediates in this ORR and propose simple kinetic models that give semiquantitative agreement with all experiments. Our results show that mrGO is semiconducting and cannot support the conventional mechanism of coherently coupled proton–electron transfers. The conducting P50 provides electrons for initiating the ORR via outer sphere electron transfer to O₂(aq), while the semiconducting mrGO provides the active catalytic sites for adsorption of O₂^–(aq) or HO₂(aq), depending upon electrolyte pH. Due to this unique synergistic effect, we describe the mrGO/P50 as a co-catalyst. Lastly, this concept implies departure from the traditional picture of predicting catalytic activity trends based on a single descriptor, and the co-catalyst design strategy may generally enable other semiconductors to function as electrocatalysts as well.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1493410

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 8; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

Chemically Derived Graphene Oxide: Towards Large-Area Thin-Film Electronics and Optoelectronics Eda, Goki; Chhowalla, Manish Advanced Materials, Vol. 22, Issue 22, p. 2392-2415 https://doi.org/10.1002/adma.200903689	journal	June 2010
Reaction Rates of Isotopic Molecules. VonL. Melander undW. H. Saunders, Jr. Wiley, New York 1980. XIV, 391 S., geb. £ 16.30 Winkler, F. J. Angewandte Chemie, Vol. 93, Issue 2 https://doi.org/10.1002/ange.19810930231	journal	February 1981
Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process Campos-Martin, Jose M.; Blanco-Brieva, Gema; Fierro, Jose L. G. Angewandte Chemie International Edition, Vol. 45, Issue 42 https://doi.org/10.1002/anie.200503779	journal	October 2006
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Tafel slopes from first principles Fletcher, Stephen Journal of Solid State Electrochemistry, Vol. 13, Issue 4 https://doi.org/10.1007/s10008-008-0670-8	journal	October 2008
High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira Nano Research, Vol. 10, Issue 4 https://doi.org/10.1007/s12274-016-1347-8	journal	November 2016
Electrocatalysts for O2 reduction Yeager, E. Electrochimica Acta, Vol. 29, Issue 11 https://doi.org/10.1016/0013-4686(84)85006-9	journal	November 1984
Isotope and surface preparation effects on alkaline dioxygen reduction at carbon electrodes Xu, Jun; Huang, Wenhua; McCreery, Richard L. Journal of Electroanalytical Chemistry, Vol. 410, Issue 2 https://doi.org/10.1016/0022-0728(96)04545-7	journal	July 1996
Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction Hartnig, Christoph; Koper, Marc T. M. Journal of Electroanalytical Chemistry, Vol. 532, Issue 1-2 https://doi.org/10.1016/S0022-0728(02)00970-1	journal	September 2002
Direct synthesis of hydrogen peroxide from hydrogen and oxygen: An overview of recent developments in the process Samanta, Chanchal Applied Catalysis A: General, Vol. 350, Issue 2 https://doi.org/10.1016/j.apcata.2008.07.043	journal	November 2008
Pseudopotentials for high-throughput DFT calculations Garrity, Kevin F.; Bennett, Joseph W.; Rabe, Karin M. Computational Materials Science, Vol. 81 https://doi.org/10.1016/j.commatsci.2013.08.053	journal	January 2014
Ab initio molecular simulations with numeric atom-centered orbitals Blum, Volker; Gehrke, Ralf; Hanke, Felix Computer Physics Communications, Vol. 180, Issue 11 https://doi.org/10.1016/j.cpc.2009.06.022	journal	November 2009
Kinetic isotope effect in the oxygen reduction reaction (ORR) over Fe-N/C catalysts under acidic and alkaline conditions Malko, Daniel; Kucernak, Anthony Electrochemistry Communications, Vol. 83 https://doi.org/10.1016/j.elecom.2017.09.004	journal	October 2017
Oxygen electroreduction on Ag(111): The pH effect Blizanac, B. B.; Ross, P. N.; Markovic, N. M. Electrochimica Acta, Vol. 52, Issue 6 https://doi.org/10.1016/j.electacta.2006.06.047	journal	January 2007
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction Kulkarni, Ambarish; Siahrostami, Samira; Patel, Anjli Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00488	journal	December 2017
Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts Pegis, Michael L.; Wise, Catherine F.; Martin, Daniel J. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00542	journal	December 2017
Observation of an Inverse Kinetic Isotope Effect in Oxygen Evolution Electrochemistry Tse, Edmund C. M.; Hoang, Thao T. H.; Varnell, Jason A. ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01170	journal	August 2016
Molecular-Level Insights into Oxygen Reduction Catalysis by Graphite-Conjugated Active Sites Ricke, Nathan D.; Murray, Alexander T.; Shepherd, James J. ACS Catalysis, Vol. 7, Issue 11 https://doi.org/10.1021/acscatal.7b03086	journal	October 2017
Toward the Decentralized Electrochemical Production of H ₂ O ₂ : A Focus on the Catalysis Yang, Sungeun; Verdaguer-Casadevall, Arnau; Arnarson, Logi ACS Catalysis, Vol. 8, Issue 5 https://doi.org/10.1021/acscatal.8b00217	journal	March 2018
Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide Chen, Shucheng; Chen, Zhihua; Siahrostami, Samira ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 1 https://doi.org/10.1021/acssuschemeng.7b02517	journal	November 2017
Advanced Carbon Electrode Materials for Molecular Electrochemistry McCreery, Richard L. Chemical Reviews, Vol. 108, Issue 7, p. 2646-2687 https://doi.org/10.1021/cr068076m	journal	July 2008
Metal-Free Catalysts for Oxygen Reduction Reaction Dai, Liming; Xue, Yuhua; Qu, Liangti Chemical Reviews, Vol. 115, Issue 11 https://doi.org/10.1021/cr5003563	journal	May 2015
Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications Wang, Haibo; Maiyalagan, Thandavarayan; Wang, Xin ACS Catalysis, Vol. 2, Issue 5 https://doi.org/10.1021/cs200652y	journal	April 2012
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Mechanism of the disproportionation of superoxide radicals Bielski, Benon H. J.; Allen, Augustine O. The Journal of Physical Chemistry, Vol. 81, Issue 11 https://doi.org/10.1021/j100526a005	journal	June 1977
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts Fukushima, Tomohiro; Drisdell, Walter; Yano, Junko Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b06737	journal	August 2015
Thermal Fluctuations of the Unusually Symmetric and Stable Superoxide Tetrahydrate Complex: An ab Initio Molecular Dynamics Study Kuo, I-Feng W.; Tobias, Douglas J. The Journal of Physical Chemistry A, Vol. 106, Issue 46 https://doi.org/10.1021/jp026873s	journal	November 2002
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp063552y	journal	August 2006
Unifying Kinetic and Thermodynamic Analysis of 2 e ^– and 4 e ^– Reduction of Oxygen on Metal Surfaces Hansen, Heine A.; Viswanathan, Venkatasubramanian; Nørskov, Jens K. The Journal of Physical Chemistry C, Vol. 118, Issue 13 https://doi.org/10.1021/jp4100608	journal	March 2014
Structure of Graphite Oxide Revisited ^‖ Lerf, Anton; He, Heyong; Forster, Michael The Journal of Physical Chemistry B, Vol. 102, Issue 23 https://doi.org/10.1021/jp9731821	journal	June 1998
Unifying the 2e ^– and 4e ^– Reduction of Oxygen on Metal Surfaces Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan The Journal of Physical Chemistry Letters, Vol. 3, Issue 20 https://doi.org/10.1021/jz301476w	journal	September 2012
Electronic Transport Properties of Individual Chemically Reduced Graphene Oxide Sheets Gomez-Navarro, Cristina; Weitz, R. Thomas; Bittner, Alexander M. Nano Letters, Vol. 7, Issue 11, p. 3499-3503 https://doi.org/10.1021/nl072090c	journal	November 2007
Nanoscale Limitations in Metal Oxide Electrocatalysts for Oxygen Evolution Viswanathan, Venkatasubramanian; Pickrahn, Katie L.; Luntz, Alan C. Nano Letters, Vol. 14, Issue 10 https://doi.org/10.1021/nl502775u	journal	September 2014
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki Nature Chemistry, Vol. 3, Issue 7, p. 546-550 https://doi.org/10.1038/nchem.1069	journal	June 2011
Structural evolution during the reduction of chemically derived graphene oxide Bagri, Akbar; Mattevi, Cecilia; Acik, Muge Nature Chemistry, Vol. 2, Issue 7, p. 581-587 https://doi.org/10.1038/nchem.686	journal	June 2010
Enabling direct H2O2 production through rational electrocatalyst design Siahrostami, Samira; Verdaguer-Casadevall, Arnau; Karamad, Mohammadreza Nature Materials, Vol. 12, Issue 12 https://doi.org/10.1038/nmat3795	journal	November 2013
High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials Lu, Zhiyi; Chen, Guangxu; Siahrostami, Samira Nature Catalysis, Vol. 1, Issue 2 https://doi.org/10.1038/s41929-017-0017-x	journal	January 2018
Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts Kim, Hyo Won; Ross, Michael B.; Kornienko, Nikolay Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0044-2	journal	March 2018
Doped graphene for metal-free catalysis Kong, Xiang-Kai; Chen, Chang-Le; Chen, Qian-Wang Chem. Soc. Rev., Vol. 43, Issue 8 https://doi.org/10.1039/C3CS60401B	journal	January 2014
Electrocatalysis on gold Rodriguez, Paramaconi; Koper, Marc T. M. Phys. Chem. Chem. Phys., Vol. 16, Issue 27 https://doi.org/10.1039/C4CP00394B	journal	January 2014
Electronic and optical properties of reduced graphene oxide Lundie, Mark; Šljivančanin, Željko; Tomić, Stanko Journal of Materials Chemistry C, Vol. 3, Issue 29 https://doi.org/10.1039/C5TC00437C	journal	January 2015
Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides Hong, Wesley T.; Stoerzinger, Kelsey A.; Lee, Yueh-Lin Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/C7EE02052J	journal	January 2017
Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis Koper, Marc T. M. Chemical Science, Vol. 4, Issue 7 https://doi.org/10.1039/c3sc50205h	journal	January 2013
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235149	journal	June 2012
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data Tkatchenko, Alexandre; Scheffler, Matthias Physical Review Letters, Vol. 102, Issue 7 https://doi.org/10.1103/PhysRevLett.102.073005	journal	February 2009
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Oxygen-Driven Unzipping of Graphitic Materials Li, Je-Luen; Kudin, Konstantin N.; McAllister, Michael J. Physical Review Letters, Vol. 96, Issue 17 https://doi.org/10.1103/PhysRevLett.96.176101	journal	May 2006
Elucidation of the Mechanism of Dioxygen Reduction on Metal-Free Carbon Electrodes Yang, Hsueh-Hui; McCreery, Richard L. Journal of The Electrochemical Society, Vol. 147, Issue 9 https://doi.org/10.1149/1.1393915	journal	January 2000
Elementary Mechanisms in Electrocatalysis: Revisiting the ORR Tafel Slope Holewinski, Adam; Linic, Suljo Journal of The Electrochemical Society, Vol. 159, Issue 11 https://doi.org/10.1149/2.022211jes	journal	January 2012

Cited By (1)

2D Electrocatalysts for Converting Earth‐Abundant Simple Molecules into Value‐Added Commodity Chemicals: Recent Progress and Perspectives Yin, Huajie; Dou, Yuhai; Chen, Shan Advanced Materials https://doi.org/10.1002/adma.201904870	journal	October 2019

Similar Records

Molecular-Level Insights into Oxygen Reduction Catalysis by Graphite-Conjugated Active Sites

Journal Article · 2017 · ACS Catalysis · OSTI ID:1557810

Ricke, Nathan D.; Murray, Alexander T.; Shepherd, James J.; +4 more

Mechanisms of Two-Electron and Four-Electron Electrochemical Oxygen Reduction Reactions at Nitrogen-Doped Reduced Graphene Oxide

Journal Article · 2019 · ACS Catalysis · OSTI ID:1605369

Kim, Hyo Won; Bukas, Vanessa J.; Park, Hun; +10 more

Optimizing the Synthetic Potential of O₂: Implications of Overpotential in Homogeneous Aerobic Oxidation Catalysis

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:2274926

Stamoulis, Alexios G.; Bruns, David L.; Stahl, Shannon S.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
graphene
hydrogen peroxide
kinetic isotope effect
mechanism
oxygen reduction reaction
pH
reaction order
superoxide

Title: Combining Experiment and Theory To Unravel the Mechanism of Two-Electron Oxygen Reduction at a Selective and Active Co-catalyst

Citation Formats

References (52)

Cited By (1)

Similar Records

Related Subjects