Jeffrey Greeley

Purdue University West Lafayette

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Zhenhua Zeng

Purdue University West Lafayette

Larry A. Curtiss

Argonne National Laboratory

Maria K. Y. Chan

Argonne National Laboratory

Jeffrey T. Miller

Purdue University West Lafayette

Jeffrey W. Elam

Argonne National Laboratory

Siddharth Deshpande

Purdue University West Lafayette

Robert E. Warburton

Case Western Reserve University

Fabio H. Ribeiro

Purdue University West Lafayette

W. Nicholas Delgass

Purdue University West Lafayette

Handan Yıldırım

Purdue University West Lafayette

Cooperative Institutions

Argonne National Laboratory

170

Robert Bosch (Germany)

Purdue University West Lafayette

Northwestern University

Chinese Academy of Sciences

Alex's Lemonade Stand Foundation

University of Illinois Urbana-Champaign

University of Illinois Chicago

University of Chicago

Technical University of Denmark

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Unique Electrochemical Adsorption Properties of Pt‐Skin Surfaces

Angewandte Chemie International Edition (2012)

Dennis F. Van der Vliet Chao Wang Dongguo Li A. P. Paulikas Jeffrey Greeley

Thin skin: Pt-alloy catalysts, such as annealed Pt3Ni(111) (see STM image; color changes mark a single atomic step), with a surface layer of pure platinum, termed a Pt-skin surface, have very different electrochemical adsorption properties to monometallic Pt. The adsorption of hydrogen is largely suppressed (see CV, (—) Pt3Ni(111)-skin versus (••••) Pt(111)), making it hard to determine the electrochemically active surface area of catalysts with Pt-skin surfaces. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

10.1002/anie.201107668

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Citations (309)

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

ChemCatChem (2019)

Evan C. Wegener Brandon C. Bukowski Dali Yang Zhenwei Wu A. Jeremy Kropf

Abstract Pt−Fe intermetallic compound (IMC) catalysts, including Pt 3 Fe, PtFe and PtFe 3 , are shown to have advantageous catalytic properties similar to those reported for single‐atom alloy catalysts. Suppresion of the Pt ensembles responsible for hydrogenolysis results in high olefin selectivity during propane dehydrogenation. In situ resonant inelastic X‐ray scattering (RIXS) results and density functional theory calculations show that these changes are associated with a decrease in the average energy of the filled 5d states of Pt in the Pt−Fe intermetallic compound structures compared to monometallic Pt, accompanied by an increase in the average energy of the unfilled valence bands. The decrease in energy of the filled Pt 5d orbitals increases with increasing Fe content in the IMC, i.e. PtFe 3 >PtFe>Pt 3 Fe. These results demonstrate that by altering the stoichiometry of IMC catalysts it is possible to control both the ensemble size and electronic properties of active sites, which affords another mechanism for tuning catalytic properties, in addition to changing promoter metals. The present study demonstrates the potential of ordered intermetallic compounds as an alternative to traditional solid‐solution single‐atom alloys to serve as catalysts with well‐defined and uniform active sites.

Hydrogenolysis

Stoichiometry

10.1002/cctc.201901869

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Citations (64)

Origin of Rate and Selectivity Trends and Exceptional Yield in Sulfur-Oxidative Propane Dehydrogenation Over Supported Vanadium Catalysts

ACS Catalysis (2023)

Allison M. Arinaga Anik Biswas Xinrui Zhang Jeffrey Greeley Tobin J. Marks

Sulfur vapor (S2) is an effective alternative oxidant for propane dehydrogenation, (S)ODHP, with vanadium-based catalysts displaying promising performance and propylene selectivity significantly greater than with O2 as the oxidant (ODHP). However, a deeper mechanistic understanding of SODHP versus ODHP will be necessary for further catalytic performance. Here, we investigate these trends over vanadium catalysts supported by Al2O3, TiO2, ZrO2, and SiO2. First, support effects on V/MxOy-catalyzed SODHP are analyzed, revealing marked support effects on the catalyst reducibility and activity. The result is maximum propylene selectivity and yield of 96 and 41%, respectively, over a sulfided V/SiO2 catalyst, surpassing most metrics in the peer-reviewed ODHP literature. Second, propane overoxidation kinetic pathways for SODHP vs. ODHP are compared, revealing that, contrary to traditional oxide catalytic pathways, secondary oxidation of propylene is disfavored over sulfided surfaces. Density functional theory (DFT) analysis reveals that while the sulfided surfaces have propylene binding energies comparable to those of oxide surfaces, the former has less favorable thermodynamic barriers to deep propylene dehydrogenation pathways than the oxide surfaces. These results suggest more competitive propylene desorption vs. propylene overoxidation on sulfided surfaces leads to higher overall selectivity. Thus, SODHP is a promising catalytic alternative for propane oxidation that rivals the traditional O2-mediated approach.

Propane

Vanadium Oxide

Propene

Propylene oxide

10.1021/acscatal.3c03677

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Citations (3)

Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction

Journal of the American Chemical Society (2008)

Dušan Strmčnik Dušan Tripković Dennis Van Vliet Kee‐Chul Chang Vladimír Komanický

The development of electrocatalytic materials of enhanced activity and efficiency through careful manipulation, at the atomic scale, of the catalyst surface structure has long been a goal of electrochemists. To accomplish this ambitious objective, it would be necessary both to obtain a thorough understanding of the relationship between the atomic-level surface structure and the catalytic properties and to develop techniques to synthesize and stabilize desired active sites. In this contribution, we present a combined experimental and theoretical study in which we demonstrate how this approach can be used to develop novel, platinum-based electrocatalysts for the CO electrooxidation reaction in CO(g)-saturated solution; the catalysts show activities superior to any pure-metal catalysts previously known. We use a broad spectrum of electrochemical surface science techniques to synthesize and rigorously characterize the catalysts, which are composed of adisland-covered platinum surfaces, and we show that highly undercoordinated atoms on the adislands themselves are responsible for the remarkable activity of these materials.

Atomic units

Surface structure

10.1021/ja8032185

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Citations (150)

Solvation Enthalpy Determination for Aqueous-Phase Reaction Adsorbates Using Ab Initio Molecular Dynamics-Based Structure Sampling

The Journal of Physical Chemistry C (2024)

Hee‐Joon Chun Ankita Morankar Zhenhua Zeng Jeffrey Greeley

The interplay between covalent and noncovalent interactions at the solid–liquid interface strongly influences electrocatalytic reactions. Although methods to determine the former interactions have been rigorously developed, the latter are often described with static bilayer models or similarly approximate methods. In this study, we account for the disorder and dynamics at complex electrochemical interfaces by proposing a simple theory to estimate the enthalpy of solvation for adsorbed intermediates. In a strategy reminiscent of Born–Haber cycles, the enthalpy of solvation is expressed in terms of two subprocesses: vacancy creation by water reorganization and adsorbate interaction with solvent molecules. The magnitude of the solvation enthalpy is then determined as a mean valueof hydrated adsorbate-catalyst configurations obtained from simulated annealing with ab initio molecular dynamic (AIMD) simulations. This theory can be generalized for many combinations of surfaces and adsorbates. Its application improves treatment of energetics at electrified solid–liquid interfaces as well as corresponding structure–activity–stability predictions, as demonstrated for electrochemical oxygen reduction on Pt(111) and on Fe–N–C catalysts and for ethanol electrooxidation on Pt(111).

Implicit solvation

10.1021/acs.jpcc.3c06870

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Citations (5)

Alloys of Platinum and Early Transition Metals as Oxygen Reduction Electrocatalysts

Meeting abstracts/Meeting abstracts (Electrochemical Society. CD-ROM) (2010)

Ifan E. L. Stephens Alexander S. Bondarenko Tobias Johansson Thomas F. Jaramillo Ib Chorkendorff

Abstract not Available.

10.1149/ma2010-01/9/491

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Citations (55)

Ab Initio Thermodynamic Modeling of Electrified Metal–Oxide Interfaces: Consistent Treatment of Electronic and Ionic Chemical Potentials

The Journal of Physical Chemistry C (2014)

Zhenhua Zeng Martin Hangaard Hansen Jeffrey Greeley Jan Rossmeisl Mårten E. Björketun

Solid oxide fuel cells are attractive devices in a sustainable energy context because of their fuel flexibility and potentially highly efficient conversion of chemical to electrical energy. The performance of the device is to a large extent determined by the atomic structure of the electrode–electrolyte interface. Lack of atomic-level information about the interface has limited the fundamental understanding, which further limits the opportunity for optimization. The atomic structure of the interface is affected by electrode potential, chemical potential of oxygen ions, temperature, and gas pressures. In this paper we present a scheme to determine the metal–oxide interface structure at a given set of these environmental parameters based on quantum chemical calculations. As an illustration we determine the structure of a Ni-YSZ anode as a function of electrode potential at 0 and 1000 K. We further describe how the structural information can be used as a starting point for accurate calculations of the kinetics of fuel oxidation reactions, in particular the hydrogen oxidation reaction. More generally, we anticipate that the scheme will be a valuable theoretical tool to describe solid–solid electrochemical interfaces.

10.1021/jp507519a

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Citations (11)

Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects

Science (2010)

Lei Yu Faisal Mehmood Sungsik Lee Jeffrey Greeley Byeongdu Lee

Production of the industrial chemical propylene oxide is energy-intensive and environmentally unfriendly. Catalysts based on bulk silver surfaces with direct propylene epoxidation by molecular oxygen have not resolved these problems because of substantial formation of carbon dioxide. We found that unpromoted, size-selected Ag3 clusters and approximately 3.5-nanometer Ag nanoparticles on alumina supports can catalyze this reaction with only a negligible amount of carbon dioxide formation and with high activity at low temperatures. Density functional calculations show that, relative to extended silver surfaces, oxidized silver trimers are more active and selective for epoxidation because of the open-shell nature of their electronic structure. The results suggest that new architectures based on ultrasmall silver particles may provide highly efficient catalysts for propylene epoxidation.

Propylene oxide

Carbon fibers

Nanometre

10.1126/science.1185200

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Citations (840)

Solvation enthalpy determination for aqueous-phase reaction adsorbates from first principles ab initio molecular dynamics

Hee‐Joon Chun Ankita Morankar Zhenhua Zeng Jeffrey Greeley

The interplay between covalent and non-covalent interactions at the solid-liquid interface strongly influences electrocatalytic reactions. Although methods to determine the former interactions have been rigorously developed, the latter are often described with static bilayer models or similarly approximate methods. In this study, we account for disorder and dynamics at complex electrochemical interfaces by proposing a simple theory to estimate the enthalpy of solvation for adsorbed intermediates. In a strategy reminiscent of Born-Haber cycles, the enthalpy of solvation is expressed in terms of two sub-processes: vacancy creation by water reorganization, and adsorbate interaction with solvent molecules. The magnitude of the solvation enthalpy is then determined as a mean value from statistical sampling of hydrated adsorbate-catalyst configurations obtained from simulated annealing with ab initio molecular dynamic (AIMD) simulations. This theory is generalizable for many combinations of surfaces and adsorbates. Its application improves treatment of energetics at electrified solid-liquid interfaces, as well as corresponding structure-activity-stability predictions, as demonstrated for electrochemical oxygen reduction on Pt(111) and on Fe-N-C catalysts and for ethanol electrooxidation on Pt(111).

Implicit solvation

10.26434/chemrxiv-2023-mxdcf

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Citations (1)

(Invited) A Reversible Lithium-Air Battery with Low Charge Polarization using Ether-Based Electrolytes

Meeting abstracts/Meeting abstracts (Electrochemical Society. CD-ROM) (2012)

Khalil Amine Jun Lü Hun‐Gi Jung Kah Chun Lau Zhangcheng Zhang

Abstract not Available.

10.1149/ma2012-02/11/1117

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Citations (0)