Water as a Promoter and Catalyst for Dioxygen Electrochemistry in

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Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media Jakub S.-Jirkovsky, Ram Subbaraman, Dusan Strmcnik, Katharine L. Harrison, Charles E. Diesendruck, Rajeev S. Assary, Otakar Frank, Lukáš Kobr, Gustav K.H. Wiberg, Bostjan Genorio, Justin G. Connell, Pietro Papa Lopes, Vojislav Stamenkovic, Larry A Curtiss, Jeffrey S. Moore, Kevin R. Zavadil, and Nenad M. Markovic ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.5b01779 • Publication Date (Web): 30 Sep 2015 Downloaded from http://pubs.acs.org on October 1, 2015

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Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media Jakub S. Jirkovský†, Ram Subbaraman†, Dusan Strmcnik†, Katharine L. Harrison‡, Charles E. Diesendruck¶, Rajeev Assary†, Otakar Frank#, Lukáš Kobr+, Gustav K. H. Wiberg†, Bostjan Genorio†,=, Justin G. Connell†, Pietro P. Lopes†, Vojislav R. Stamenkovic†, Larry Curtiss†, Jeffrey S. Moore¶, Kevin R. Zavadil‡ and Nenad M. Markovic†* †

Materials Science Division, Argonne National Laboratory, Argonne, IL, USA

‡

Sandia National Laboratory, Albuquerque, NM, USA

¶

University of Illinois at Urbana-Champaign, Urbana, IL, USA

+ Northwestern University, Evanston, IL, USA #J. Heyrovsky Institute of Physical Chemistry, Prague, Czech Republic = University of Ljubljana, Faculty of Chemistry and Chemical Technology, Ljubljana, Slovenia

Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultra-dry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad···H2O (aqueous solutions) and LiO2···H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that even at low concentrations ( Pt(111) >Au (111) with Pt3Ni(111) being the most active catalyst for the ORR ever observed in aqueous environments; (c) schematic of a proposed OHad-H2O complex (“activated water”) formed via hydrogen bonding emphasizing that this complex might be a key descriptor for controlling the reaction pathway of the ORR in aqueous environments.

(d) schematic

representation of the effect of “activated water” on peroxide and hydroxyl formation on surfaces with a low coverage of OHad-H2O complexes; (e) schematic representation of further peroxide reduction on a surface covered with two active OHad centers that are required for the peroxide OO bond cleavage and final production of three hydroxyl ions. Note that schematics are meant to illustrate the most probable reaction pathway for the ORR based on the results presented.

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Figure 3. Water effect on oxygen electrochemistry in a presence of Li+: water as a promotor and catalyst. (a) CV of Au(100) in dry DME 0.3M TBAPF6 saturated with O2 and various concentrations of Li+; (b) CV in O2 saturated 0.1M Li triflate for Au(100) and Au(111) and (c) the effect of various amounts of water on Li-O2 electrochemistry on Au(100) (sweep rate = 100 mV s-1). (d) in situ AFM imaging of Au(111) in TEGDME/LiClO4 saturated with O2 at 3.5V and (e) held at 2.5V for 30 min.; (f) in situ Raman spectroscopy of a roughened gold electrode at 2.5V in “dry” (1ppm of H2O) and “wet” (40 ppm of H2O) electrolyte (DME, 0.1M LiClO4). The vertical lines are added to guide the eye. See also Supplementary Figure S4 and Supplementary Information for additional details on Raman bands assignment.


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Figure 4. Water as catalyst and promoter in Li-O2 electrochemistry. (a) Schematics of LiO2H2O complex formation through dipole-dipole electrostatic forces, formation of “activated water” required for protonation of O2- and formation of Li-based deposits in ether-based electrolytes. For LiO2 and Li2O2 formation the proposed schematics involves four steps: (i) LiO2 formation (steps 1 and 2); (ii) formation of the LiO2---OH2 complex through dipole-dipole interaction in steps 2-3 (iii) interaction of the LiO2---OH2 complex with superoxide in steps 3 to 4; (iv) proton and electron transfer to the superoxide molecule to form hydrogen peroxide and finally in steps 4 and 5; and (v) formation of Li2O2 and regeneration of water (water as catalyst). The slabs are added to illustrate that the processes are taking place at an electrode surface acting simultaneously as proton donor. The direction of the arrows follow the flow of electrons.


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The effect of water on superoxo electrochemistry on Au(hkl) in ether-based electrolytes. (a) Cyclic voltammetry (CV) on Au(hkl) in dry DME, 0.3M TBAPF6 (>Au(100) > Pt(111) >Au (111) with Pt3Ni(111) being the most active catalyst for the ORR ever observed in aqueous environments; (c) schematic of a proposed OHad-H2O complex (“activated water”) formed via hydrogen bonding emphasizing that this complex might be a key descriptor for controlling the reaction pathway of the ORR in aqueous environments. (d) schematic representation of the effect of “activated water” on peroxide and hydroxyl formation on surfaces with a low coverage of OHad-H2O complexes; (e) schematic representation of further peroxide reduction on a surface covered with two active OHad centers that are required for the peroxide O-O bond cleavage and final production of three hydroxyl ions. Note that schematics are meant to illustrate the most probable reaction pathway for the ORR based on the results presented. 233x153mm (300 x 300 DPI)

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Water effect on oxygen electrochemistry in a presence of Li+: water as a promotor and catalyst. (a) CV of Au(100) in dry DME 0.3M TBAPF6 saturated with O2 and various concentrations of Li+; (b) CV in O2 saturated 0.1M Li triflate for Au(100) and Au(111) and (c) the effect of various amounts of water on Li-O2 electrochemistry on Au(100) (sweep rate = 100 mV s-1). (d) in situ AFM imaging of Au(111) in TEGDME/LiClO4 saturated with O2 at 3.5V and (e) held at 2.5V for 30 min.; (f) in situ Raman spectroscopy of a roughened gold electrode at 2.5V in “dry” (1ppm of H2O) and “wet” (40 ppm of H2O) electrolyte (DME, 0.1M LiClO4). The vertical lines are added to guide the eye. See also Supplementary Figure S4 and Supplementary Information for additional details on Raman bands assignment. 249x120mm (300 x 300 DPI)


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Water as catalyst and promoter in Li-O2 electrochemistry. (a) Schematics of LiO2-H2O complex formation through dipole-dipole electrostatic forces, formation of “activated water” required for protonation of O2- and formation of Li-based deposits in ether-based electrolytes. For LiO2 and Li2O2 formation the proposed schematics involves four steps: (i) LiO2 formation (steps 1 and 2); (ii) formation of the LiO2---OH2 complex through dipole-dipole interaction in steps 2-3 (iii) interaction of the LiO2---OH2 complex with superoxide in steps 3 to 4; (iv) proton and electron transfer to the superoxide molecule to form hydrogen peroxide and finally in steps 4 and 5; and (v) formation of Li2O2 and regeneration of water (water as catalyst). The slabs are added to illustrate that the processes are taking place at an electrode surface acting simultaneously as proton donor. The direction of the arrows follow the flow of electrons. 212x141mm (300 x 300 DPI)


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Water as a Promoter and Catalyst for Dioxygen Electrochemistry in

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