First principles theories of interfacial science and catalysis

The properties of interfaces determine many of the macroscopic characteristics of a broad range of important engineering materials, from heterogeneous catalysts to batteries, and in recent years, first principles calculations have emerged as powerful tools for elucidating these properties at the atomic scale. These ab initio calculations are capable of determining structural and energetic properties of interfaces that are difficult, if not impossible, to access experimentally, and in some cases, the calculations have been used to identify new materials with superior properties.

In the Greeley group, we combine first principles calculations of interfaces with classical thermodynamic and kinetic theories to predict macroscopic catalytic and materials properties. We apply these general techniques to several specific classes of interfaces, with an ultimate goal of understanding and designing materials from first principles. Specific areas of interest include:

1) Heterogeneous catalysis. One of our primary focus areas is the complex chemistry of biomass conversion to hydrogen and to liquid fuels on metal surfaces; in particular, we seek to develop accelerated strategies for modeling these reaction networks with first principles calculations. An additional interest is in determining how the interactions between nanoparticle catalysts and oxide supports can, in some cases, lead to novel reactivity patterns that are not observable on either the nanoparticle or the support in isolation.

2) Electrocatalysis. We apply surface science-based techniques, which have been extensively studied at gas-solid interfaces, to probe the fundamental mechanistic details electrocatalytic processes that occur in fuel cells and electrolyzers. We also focus on developing models of the stability of metal/liquid interfaces in electrocatalytic environments; our goal, in this work, is to determine the durability of fuel cells during extended periods of operation.

3) Energy storage in batteries. Although battery technology has been deployed commercially for many years, the fundamental science and engineering of electrode/electrolyte interfaces in batteries is still poorly understood. Our work in this area focuses on the study of lithiation of next-generation anode materials for lithium ion batteries, with an ultimate goal of both predicting higher capacity battery materials and understanding the processes that degrade these materials over long cycle periods.

We are a part of the Purdue Catalysis Center, which fosters interaction among faculty and students in catalysis research groups by collaborating on research projects, sharing resources and facilities, and holding weekly joint group meetings.

"Defect-Mediated Ordering of Condensed Water Structures in Microporous Zeolites", B. C. Bukowski, J.S. Bates, R. Gounder, J. Greeley, Angewandte Chemie 10.1002/anie.201908151 (2019)

"Nonprecious Metal Catalysts for Tuning Discharge Product Distribution at Solid-Solid Interfaces of Aprotic Li-O2 Batteries", Samji Samira, Siddharth Deshpande, Charles A. Roberts, Ayad M. Nacy, Joseph Kubal, Kristian Matesic, Owen Oesterling, Jeffrey Greeley, and Eranda Nikolla, Chem. Mater. 10.1021/acs.chemmater.9b01817 (2019)

"Tunable intrinsic strain in two-dimensional transition metal electrocatalysts", Wang, L.; Zeng, Z.; Gao, W.; Maxson, T.; Raciti, D.; Giroux, M.; Pan, X.; Wang, C.; Greeley, J., Science 363 (6429), 870-874 10.1126/science.aat8051 (2019)

"Operando Observations and First-Principles Calculations of Reduced Bulk Lithium Insertion in Au-Coated LiMn2O4", K.L. Bassett, R.E. Warburton, S. Deshpande, T.T. Fister, K. Ta, J.L. Esbenshade, A. Kinaci, M.K.Y. Chan, K.M. Wiaderek, K.W. Chapman, J.P. Greeley, A.A. Gewirth, Advanced Materials Interfaces 6(4) 1801923 10.1002/admi.201801923 (2019)

"Understanding the Role of Overpotentials in Lithium Ion Conversion Reactions: Visualizing the Interface", G. Evmenenko, R.E. Warburton, H. Yildirim, J. Greeley, M.K.Y. Chan, D.B. Buchholz, P. Fenter, M.J. Bedzyk, T.T. Fister , ACS Nano 13(7) 7825-7832 10.1021/acsnano.9b02007 (2019)

"Cooperative Effects Between Hydrophilic Pores and Solvents: Catalytic Consequences of Hydrogen-Bonding on Alkene Epoxidation in Zeolites", D. T. Bregante, A. M. Johnson, A, Y. Patel, E. Z. Ayla, M. J. Cordon, B. C. Bukowski, J. Greeley, R. Gounder, D. W. Flaherty*, Journal of the American Chemical Society, 141 7302-7319 doi.org/10.1021/jacs.8b12861 (2019)

"Distinct Catalytic Reactivity of Sn Substituted in Framework Locations and at Defect Grain Boundaries in Sn-Zeolites", J. S. Bates, B. C. Bukowski, J. W. Harris, J. Greeley, R. Gounder*, ACS Catalysis DOI: 10.1021/acscatal.9b01123 (2019)

"High Rate Spinel LiMn2O4 (LMO) Following Carbonate Removal and Formation of Li-rich Interface by ALD Treatment", M.J. Young, S. Letourneau, R.E. Warburton, W.M. Dose, C.S. Johnson, J.P. Greeley, J.W. Elam, The Journal of Physical Chemistry C, DOI: 10.1021/acs.jpcc.9b04418 (2019)

"Mechanism for Al2O3 Atomic Layer Deposition on LiMn2O4 from In Situ Measurement and Ab Initio Calculations" L. Chen, R.E. Warburton, K.-S. Chen, J.A. Liberia, C. Johnson, Z. Yang, M.C. Hersam, J.P. Greeley, J.W. Elam, Chem 4(10) 2418-2435 doi.org/10.1016/j.chempr.2018.08.006 (2018)

"Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks" Chong, L., Wen, J., Kubal, J., Sen, F. G., Zou, J., Greeley, J., Liu, D. J. Science 10.1126/science.aau0630 (2018)

"Changes in Catalytic and Adsorptive Properties of 2 nm Pt3Mn Nanoparticles by Subsurface Atoms," Z. Wu, B.C. Bukowski, Z. Li, C. Milligan, L. Zhou, T. Ma, Y. Wu, Y. Ren, F.H. Ribeiro, W.N. Delgass, J. Greeley, G. Zhang, J.T. Miller, JACS, 140(44), 14870-14877. 10.1021/jacs.8b08162 (2018)

"First Principles, Microkinetic, and Experimental Analysis of Lewis Acid Site Speciation During Ethanol Dehydration on Sn-Beta Zeolites", B. C. Bukowski, J. S. Bates, R. Gounder, J. Greeley*, Journal of Catalysis, 365 261-276 doi.org/10.1016/j.jcat.2018.07.012 (2018)

"Generalized scaling relationships on transition metals: Influence of adsorbate-coadsorbate interactions." Majumdar, P., & Greeley, J. Physical Review Materials, 2(4), 45801. https://doi.org/10.1103/PhysRevMaterials.2.045801 (2018)

"Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates. Choksi, T., Majumdar, P., & Greeley, J. P. Angewandte Chemie, 130(47), 15636-15640. https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201808246 (2018)