Reshma R. Rao
Massachusetts Institute of Technology
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Featured researches published by Reshma R. Rao.
Science | 2017
Jonathan Hwang; Reshma R. Rao; Livia Giordano; Yu Katayama; Yang Yu; Yang Shao-Horn
Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.
Energy and Environmental Science | 2017
Reshma R. Rao; Manuel Kolb; Niels Bendtsen Halck; Anders Filsøe Pedersen; Apurva Mehta; Hoydoo You; Kelsey A. Stoerzinger; Zhenxing Feng; Heine Anton Hansen; Hua Zhou; Livia Giordano; Jan Rossmeisl; Tejs Vegge; Ib Chorkendorff; Ifan E. L. Stephens; Yang Shao-Horn
While the surface atomic structure of RuO2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H2O on the coordinatively unsaturated Ru sites (CUS) and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.
Topics in Catalysis | 2018
Kelsey A. Stoerzinger; Xiao Renshaw Wang; Jonathan Hwang; Reshma R. Rao; Wesley T. Hong; Christopher M. Rouleau; Dongwook Lee; Yi Yu; Ethan J. Crumlin; Yang Shao-Horn
Cobalt-containing perovskite oxides are promising electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolyzers. However, a lack of fundamental understanding of oxide surfaces impedes rational catalyst design for improved activity and stability. We couple electrochemical studies of epitaxial La1−xSrxCoO3−δ films with in situ and operando ambient pressure X-ray photoelectron spectroscopy to investigate the surface stoichiometry, adsorbates, and electronic structure. In situ investigations spanning electrode compositions in a humid environment indicate that hydroxyl and carbonate affinity increase with Sr content, leading to an increase in binding energy of metal core levels and the valence band edge from the formation of a surface dipole. The maximum in hydroxylation at 40% Sr is commensurate with the highest OER activity, where activity scales with greater hole carrier concentration and mobility. Operando measurements of the 20% Sr-doped oxide in alkaline electrolyte indicate that the surface stoichiometry remains constant during OER, supporting the idea that the oxide electrocatalyst is stable and behaves as a metal, with the voltage drop confined to the electrolyte. Furthermore, hydroxyl and carbonate species are present on the electrode surface even under oxidizing conditions, and may impact the availability of active sites or the binding strength of adsorbed intermediates via adsorbate–adsorbate interactions. For covalent oxides with facile charge transfer kinetics, the accumulation of hydroxyl species with oxidative potentials suggests the rate of reaction could be limited by proton transfer kinetics. This operando insight will help guide modeling of self-consistent oxide electrocatalysts, and highlights the potential importance of carbonates in oxygen electrocatalysis.
Catalysis Today | 2016
Livia Giordano; Binghong Han; Marcel Risch; Wesley T. Hong; Reshma R. Rao; Kelsey A. Stoerzinger; Yang Shao-Horn
ACS energy letters | 2017
Kelsey A. Stoerzinger; Oscar Diaz-Morales; Manuel Kolb; Reshma R. Rao; Rasmus Frydendal; Liang Qiao; Xiao Renshaw Wang; Niels Bendtsen Halck; Jan Rossmeisl; Heine Anton Hansen; Tejs Vegge; Ifan E. L. Stephens; Marc T. M. Koper; Yang Shao-Horn
Chem | 2017
Kelsey A. Stoerzinger; Reshma R. Rao; Xiao Renshaw Wang; Wesley T. Hong; Christopher M. Rouleau; Yang Shao-Horn
Joule | 2017
Denis A. Kuznetsov; Binghong Han; Yang Yu; Reshma R. Rao; Jonathan Hwang; Yuriy Román-Leshkov; Yang Shao-Horn
Chemistry of Materials | 2017
Kelsey A. Stoerzinger; Wesley T. Hong; Xiao Renshaw Wang; Reshma R. Rao; Srinivas Bengaluru Subramanyam; Changjian Li; Ariando; T. Venkatesan; Qiang Liu; Ethan J. Crumlin; Kripa K. Varanasi; Yang Shao-Horn
Journal of Physical Chemistry C | 2018
Reshma R. Rao; Manuel Kolb; Jonathan Hwang; Anders Gorm Pedersen; Apurva Mehta; Hoydoo You; Kelsey A. Stoerzinger; Zhenxing Feng; Hua Zhou; Hendrik Bluhm; Livia Giordano; Ifan E. L. Stephens; Yang Shao-Horn
Journal of Physical Chemistry C | 2018
Jonathan Hwang; Reshma R. Rao; Yu Katayama; Dongkyu Lee; Xiao Renshaw Wang; Ethan J. Crumlin; T. Venkatesan; Ho Nyung Lee; Yang Shao-Horn