1. CISTAR: NSF Center for Innovative and Strategic Transformation of Alkane Resources

The goal of this engineering research center (ERC) is to create a transformative engineered system to convert light hydrocarbons from shale resources to chemicals and transportation fuels in smaller, modular, local, and highly networked processing plants. For more details, click here to visit the center website

2. Data Science-Driven Discovery of Multimetallic Oxygen-Cycle Electrocatalysts

Combine material informatics with rigorous first principles analyses and molecular-level characterization to probe the catalyst structure and reactivity of novel multimetallic high-entropy alloys (HEA). The effort involves identification of in-situ mechanisms for degradation and transformation of catalysts with highly complex catalytic structures, and the impact of these transformations on catalytic activity. These techniques are researched with application to energy-critical oxygen cycle electrocatalytic reactions, including oxygen reduction (ORR) and oxygen evolution (OER) reactions.

• Jeffrey Greeley: DFT calculations, material-informatics method development
• Jeffrey Miller: Experimental kinetics and spectroscopic measurements
• Chao Wang (John Hopkins University): Kinetics and spectroscopic measurements
• Yannis Kevrekidis (John Hopkins University): Multi-scale model development
• Liangbing Hu (Maryland University): Synthesis, characterisation, and kinetic measurements

• Zeng, Z.; Chang, K.-C.; Kubal, J.; Markovic, N.; Greeley, J. Stabilization of Ultrathin (Hydroxy)oxide Films on Transition Metal Substrates for Electrochemical Energy Conversion. Nature Energy 2017, 2, 17070
• Kevrekidis, I. G.; Gear, C. W.; Hyman, J. M.; Kevrekidis, P. G.; Runborg, O.; Theodoropoulos, K. Equation-free coarse-grained multiscale computation: enabling microscopic simulators to perform system-level tasks. Comm. Mat. Sciences 2003, 1, 715-762.
• Yao, Y. G.; Huang, Z. N.; Xie, P. F.; Lacey, S. D.; Jacob, R. J.; Xie, H.; Chen, F. J.; Nie, A. M.; Pu, T. C.; Rehwoldt, M.; Yu, D. W.; Zachariah, M. R.; Wang, C.; Shahbazian-Yassar, R.; Li, J.; Hu, L. B. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science 2018, 359, 1489-1494.

3. Design of Selective Oxidation Catalysts using Transition Metal Zeolites (top)

Zeolites exchanged with transition metals, such as copper and iron, are known to catalyze a range of oxidation reactions, including partial methane oxidation. The transition metal active site complexes that are formed depend on zeolite structural properties such as Al density and proximity, as well as the conditions used for metal exchange and subsequent gas-phase activation treatments. This research combines synthetic manipulation of zeolitic materials, experimental characterization to probe the metal active sites involved in selective oxidation reactions, and theoretical calculations to corroborate and connect with experimental findings.

• Rajamani Gounder: Experimental synthesis, characterization and kinetic measurements
• Jeffrey Miller: Experimental kinetics and spectroscopic measurements
• William Schneider (University of Notre Dame): DFT calculations, AIMD simulations

• H. Li^, C. Paolucci^, I. Khurana, L. N. Wilcox, F. Göltl, J.D. Albarracin-Caballero, A. J. Shih, F. H. Ribeiro, R. Gounder, W. F. Schneider*, “Consequences of Exchange-Site Heterogeneity and Dynamics on the UV-Visible Spectrum of Cu-Exchanged SSZ-13", Chemical Science 10(2019) 2373-2384
• D. T. Bregante, L. N. Wilcox, C. Liu, C. Paolucci, R. Gounder and D. W. Flaherty, “Dioxygen Activation Kinetics over Distinct Cu Site Types in Cu-Chabazite Zeolites", ACS Catal., 2021, 11, 11873–11884

4. Electrochemical Applications of Ruddlesden-Popper Oxides (top)

Ruddlesden-Popper (RP) oxides are a class of highly tunable mixed metal oxides, which are of the general formula A_n+1B_nO_3n+1 (n = 1, 2, 3… ; A = rare earth/alkaline earth; B = transition metal). This tunability has been effectively leveraged to discover new catalysts for oxygen electrochemistries, such as, oxygen reduction and evolution reactions taking place in fuel cells and Li-air batteries. The goal of this work is to implement coupled theory-experiment effort to understand the electronic structure to fundamentally understand the underlying principles and develop structure-property relationships which will aid in catalysts discovery with aim of further reducing the charging overpotentials in Li-air batteries.

• Jeffrey Greeley: DFT calculations, material-informatics method development
• Eranda Nikolla (Wayne State University): Synthesis, electrochemical analysis and material characterization

• Von Gunten, A., Velinkar, K., Nikolla, E., and Greeley, J.; Elucidation of Parasitic Reaction Mechanisms at Interfaces in Na-O2 Batteries, Chemistry of Materials, (2023), 35(15), 5945–5952.
• Velinkar, K. K., Gunten, A. von, Greeley, J., & Nikolla, E.; Influence of the Mechanism of Discharge Product Formation on the Electrochemical Performance and Cyclability of Aprotic Na-O2 Batteries, ACS Energy Letters, (2023), 8(11), 4555–4562.
• X.K. Gu, S. Samira, E. Nikolla; Oxygen Sponges for Electrocatalysis: Oxygen Reduction/Evolution on Nonstoichiometric, Mixed Metal Oxides, Chem Mater, 30 (2018) 2860-2872.
• X.K. Gu, J.S.A. Carneiro, S. Samira, A. Das, N.M. Ariyasingha, E. Nikolla; Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides, J Am Chem Soc, 140 (2018) 8128-8137.
• S. Samira^, S. Deshpande^, Roberts, C. A., Nacy, A. M., Kubal, J., Matesić, K., Oesterling, O., Greeley J.*; Nikolla, E.*; Nonprecious Metal Catalysts for Tuning Discharge Product Distribution at Solid−Solid Interfaces of Aprotic Li−O2 Batteries, Chem. Mater. 2019, 31, 7300−7310.

5. Multiscale Design of Active Sites and Crystal Morphology in Zeolites for Precise Catalytic Transformations (top)

Bronsted acidic zeolites are remarkably diverse in structure and composition, beyond shape selective phenomena that are dictated by their framework topology. Manipulation of synthetic conditions and precursors allows for the modification of these catalysts with site-level and atomic-level precision. This project aims to build synthesis-structure-function relations to describe and predict such site and atomic level properties, by combining experimental synthesis and characterization with computational modeling of interactions between zeolite frameworks and the structure-directing agents used to crystallize them. These model materials are used to interrogate the role of acid and metal site distribution on catalytic reactions of academic and industrial interest.

• Rajamani Gounder: Experimental synthesis, characterization and kinetic measurements
• William Schneider (University of Notre Dame): DFT calculations, AIMD simulations
• David Hibbitts (Florida): DFT calculations

• Bickel, E. E.; Hoffman, A. J.; Lee, S.; Snider, H. E.; Nimlos, C. T.; Zamiechowski, N. K.; Hibbitts, D. D.; Gounder, R. Altering the Arrangement of Framework Al Atoms in MEL Zeolites Using Mixtures of Tetrabutylammonium and Sodium Structure-Directing Agents, Chem. Mater. 2022, 34 (15), 6835–6852.
• S. Lee, C. T. Nimlos, E. R. Kipp, Y. Wang, X. Gao, W. F. Schneider, M. Lusardi, V. Vattipalli, S. Prasad, A. Moini and R. Gounder, Evolution of Framework Al Arrangements in CHA Zeolites during Crystallization in the Presence of Organic and Inorganic Structure-Directing Agents, Crystal Growth & Design, 2022, 22, 6275–6295.
• C. T. Nimlos^, A. J. Hoffman, Y. G. Hur, B. J. Lee, J. R. Di Iorio, D. D. Hibbitts and R. Gounder Experimental and Theoretical Assessments of Aluminum Proximity in MFI Zeolites and Its Alteration by Organic and Inorganic Structure-Directing Agents, Chem. Mater., 2020, 32, 9277–9298
• J. R. Di Iorio^, S. Li^, C. B. Jones, C. T. Nimlos, Y. Wang, E. Kunkes, V. Vattipalli, S. Prasad, A. Moini, W. F. Schneider*, R. Gounder*, Cooperative and Competitive Occlusion of Organic and Inorganic Structure Directing Agents within Chabazite Zeolites Influences Their Aluminum Arrangement", Journal of the American Chemical Society (2020)
• J. R. Di Iorio , A. J. Hoffman , C. T. Nimlos , S. Nystrom , D. Hibbitts *, R. Gounder* "Mechanistic Origins of the High-Pressure Inhibition of Methanol Dehydration Rates in Small-Pore Acidic Zeolites" Journal of Catalysis, 380 (2019) 161-177
• Y.G. Hur^, P.M. Kester^, C.T. Nimlos, Y. Cho, J.T. Miller, R. Gounder* “Influence of Tetrapropylammonium and Ethylenediamine Structure Directing Agents on the Framework Al Distribution in B-Al-MFI Zeolites” Industrial & Engineering Chemistry Research, 58 (2019) 11849-11860
• S. Li, R. Gounder, A. Debellis, I. B. Müller, S. Prasad, A. Moini, W. F. Schneider* "Influence of N,N,N-Trimethyl-1-Adamantyl Ammonium Structure Directing Agent on Al Substitution in SSZ-13 Zeolite", Journal of Physical Chemistry C, 123 (2019) 17454-17458

6. NO_x Selective Catalytic Reduction for Automotive Exhaust Applications (top)

Copper-exchanged zeolites are used as catalysts for the selective catalytic reduction (SCR) of NO_x emissions onboard heavy-duty lean-burn engines. This effort combines kinetic measurements, in operando spectroscopy, and computational methods to characterize the active sites during catalytic turnover. These techniques are used to better understand how the kinetics of SCR reactions are influenced by different catalyst material properties, including copper structure, active site density, and zeolite framework topology.

• Rajamani Gounder: Experimental synthesis, characterization and kinetic measurements
• Fabio Ribeiro: In-operando spectroscopy
• Jeffrey Miller: In-operando spectroscopy
• William Schneider (University of Notre Dame): DFT calculations, AIMD simulations

• Krishna, S.H., Goswami, A., Wang, Y. et al. Influence of framework Al density in chabazite zeolites on copper ion mobility and reactivity during NOx selective catalytic reduction with NH3, Nat. Catal. 6, 276–285 (2023).
• DeLuca, M.; Jones, C. B.; Krishna, S. H.; Goswami, A.; Saxena, R.; Li, S.; Prasad, S.; Moini, A.; Schneider, W. F.; Gounder, R.,Effects of Zeolite Framework Topology on Cu(I) Oxidation and Cu(II) Reduction Kinetics of NOx Selective Catalytic Reduction with NH3, Chem Catalysis 2023, 3 (9), 100726.
• C. Paolucci, I. Khurana, A.A. Parekh, S. Li, A.J. Shih, H. Li, J.R.D. Iorio, J.D. Albarracin-Caballero, A. Yezerets, J.T. Miller, W.N. Delgass, F.H. Ribeiro, W.F. Schneider, R. Gounder, “Dynamic multinuclear sites formed by mobilized copper ions in NOx selective catalytic reduction”, Science, 357 (2017) 898–903
• C. Paolucci, A.A. Parekh, I. Khurana, J.R. Di Iorio, H. Li, J.D. Albarracin Caballero, A.J. Shih, T. Anggara, W.N. Delgass, J.T. Miller, F.H. Ribeiro, R. Gounder, W.F. Schneider, “Catalysis in a Cage: Condition-Dependent Speciation and Dynamics of Exchanged Cu Cations in SSZ-13 Zeolites”, J. Am. Chem. Soc. 138 (2016) 6028–6048
• S.A. Bates, A.A. Verma, C. Paolucci, A.A. Parekh, T. Anggara, A. Yezerets, W.F. Schneider, J.T. Miller, W.N. Delgass, F.H. Ribeiro, “Identification of the active Cu site in standard selective catalytic reduction with ammonia on Cu-SSZ-13”, Journal of Catalysis, 312 (2014) 87–97

7. Surface Science Study of Strong Metal-Support Interactions (top)

Strong metal-support interactions (SMSI) have been widely applied to modify supported metal nanoparticle catalysts, yet the mechanism behind this phenomenon is still elusive. This research aims at molecular-level understanding of SMSI by combining surface science characterization of model catalysts and DFT calculations.

• Jeffrey Greeley: DFT calculations, material-informatics method development
• Jeffrey Miller: Experimental kinetics and spectroscopic measurements
• Dmitry Zemlyanov: Spectroscopy, surface-science experiments

• Sawant K. J., Zeng Z., Greeley J. P., Universal properties of metal-supported oxide films from linear scaling relationships: elucidation of mechanistic origins of strong metal–support interactions, Chemical Science, 2023
• Breckner Christian J., Zhu Kuixin, Wang Mingrui, Zhang Guanghui, Li Christina W., Miller Jeffrey T., Controlled site coverage of strong metal–support interaction (SMSI) on Pd NP catalysts, Catalysis Science & Technology, 1, 157-169, 2023
• Zeng, Z.; Chang, K.-C.; Kubal, J.; Markovic, N.; Greeley, J. Stabilization of Ultrathin (Hydroxy)oxide Films on Transition Metal Substrates for Electrochemical Energy Conversion. Nature Energy 2017, 2, 17070
• Gao, J*.; Sawant, K. J*; Miller, J. T.; Zeng, Z.; Zemlyanov, D.; Greeley, J. P. Structural and Chemical Transformations of Zinc Oxide Ultrathin Films on Pd(111) Surfaces. ACS Appl. Mater. Interfaces 2021, 13 (29), 35113–35123.

8. Low-Temperature Electrocatalytic Manufacturing of Essential Chemical Building Blocks (top)

Electrocatalytic manufacturing of essential chemical building blocks could drastically reduce associated CO2 emissions by avoiding thermodynamic limitations of the thermal processing routes and by utilizing CO2-free energy from wind and solar. Electrochemical devices that are optimized for chemical processing reactions must be developed to achieve these benefits. This work aims to build the fundamental science necessary to realize this new paradigm of chemical processing by simultaneously developing new gas diffusion layer (GDL) technology, quantifying alkane reaction kinetics on electrocatalysts in aqueous environments, and discovering active and selective electrocatalyst materials with first principles calculations and data science techniques.

• Brian Tackett: Experimental electrocatalytic kinetic evaluation and electrochemical device testing
• Bryan Boudouris: Functional polymer synthesis for gas-diffusion layer development
• Rajamani Gounder: Kinetic and mechanistic analysis of electrocatalytic reactions
• Jeffrey Greeley: DFT calculations and data science material discovery
• Jeffrey Miller: Electrocatalyst synthesis and in-situ characterization