Author Archives: Carl Menning

2016-2017 Meeting Program

Thursday, Sept. 15th, 2016Dion VlachosIn Silico Prediction of Materials for Energy Applications
Dion Vlachos, University of Delaware - 2016 CCP Award Winner
Abstract » | Announcement »

Thursday, Oct. 27th, 2016Keiichi TomishigeDevelopment of heterogeneous catalysts for the production of biomass-derived chemicals by selective C-O hydrogenolysis and deoxydehydration
Keiichi Tomishige, Tohoku University
Abstract » | Announcement »

Student Speaker
Thursday, Nov. 10th, 2016Ravindra DattaUnraveling Catalytic Mechanisms and Kinetics: Lessons from Electrical Networks
Ravindra Datta, Worcester Polytechnic Institute
Abstract » | Announcement »
Graduate Student Poster Session
Thursday, Jan. 19th, 2017Ahmad MoiniCiapetta Award Lecture:
Novel Zeolite Catalysts for Diesel Emission Applications

Ahmad Moini, BASF
Abstract » | Announcement »

Student Speaker
Thursday, Feb. 16th, 2017Raul LoboBiomass and Natural Gas Valorization by Zeolite Catalysis
Raul Lobo, University of Delaware
Abstract »

Student Speaker
Officer Nominations
Thursday, Mar. 16th, 2017Manuela SerbanParallel between UOP’s Reforming and Dehydrogenation Technologies and Catalysts
Manuela Serban, Honeywell (UOP)
Abstract »
Officer Nominations
Thursday, Apr. 20th, 2017Avelino CormaSolid Catalysts Design: From Fundamental Knowledge To Catalytic Application
Avelino Corma, Instituto de Tecnología Química
Abstract »  |  Announcement »
Officer Elections
May 2017Spring Symposium
Online Dinner Reservation » | Directions to Double Tree Hotel »

2016-2017 Officers

2016-2017 Officers


Anton Petushkov
Zeolyst Inter­na­tional
Past Chair
Torren Carlson
Josh Pacheco
Zeolyst Inter­na­tional
Lifeng Wang
Zeolyst International
Dan Slanac
Program Chair
Istvan Halasz
Zeolyst International
Arrangements Chair
Tzia Ming
University of Pennsylvania
Director Membership
Jacob Dickinson
Director Poster Session
Eric Sacia
Director Sponsorship
Thomas Yeh
Johnson Matthey
Carl Menning
Sentry Data Systems
Representative to NACS
Dion Vlachos
University of Delaware

Production of para-methylstyrene and para-divinylbenzene from furanic compounds

2017 Spring Symposium

Molly Koehle and Raul Lobo, Chemical and Biomolecular Engineering, University of Delaware, Newark, DE

Abstract – Of the three isomers of methylstyrene, para-methylstyrene is highly desirable because it yields polymers with superior properties over polystyrene and mixed poly-methylstyrene [1]. However, controlling the substitution of methylstyrene via direct acylation or alkylation of toluene is difficult because even though the para isomer is favored, meta and ortho isomers are also formed [1, 2], and separation of the isomer mixture is very difficult due to their nearly identical properties.

The Diels-Alder cycloaddition and dehydration of substituted furans with ethylene is a plausible route to p-methylstyrene since it is inherently selective to para aromatic species. We have successfully developed a three-step catalytic route to p-methylstyrene from methylfuran (Scheme 1) at high yield and very high isomer selectivity. The process uses Friedel-Crafts acylation, selective reductions with hydrogen and Diels-Alder cycloaddition with ethylene. The raw materials—furans, ethylene and acetic acid—can all be derived from biomass [3,4], thus allowing ‘green’ styrene production from renewable carbon sources. This approach has also been extended to the production of p-divinylbenzene. As the acylation step is known to be catalyzed by Lewis acids, recent work has focused on studying this step on Brønsted and Lewis acid zeolites and will be presented as well.

Scheme 1: Production of para-methylstyrene from methylfuran

[1] W.W. Kaeding and G.C. Barile, in: B.M. Culbertson and C.U. Pittman, Jr. (Eds.), New Monomers and Polymers, Plenum Press, New York, NY, 1984, pp. 223-241.
[2]“Aromatic Substitution Reactions.”
[3] A.A. Rosatella; S.P. Simeonov; R.F.M. Frade, R.F.M..; C.A.M. Afonso, Green Chem., 13 (2011) 754.
[4] C.H. Christensen; J. Rass-Hansen; C.C. Marsden; E. Taarning; K. Egeblad, ChemSusChem, 1 (2008) 283.

Biography – Molly obtained her B.S. in Chemical Engineering from the University of Pittsburgh and her M.S. in Chemical Engineering from the University of Connecticut. She has worked at the Catalysis Center for Energy Innovation in Prof. Raul Lobo’s group since 2013. Her work focuses on transformations of biomass to fuels and chemicals with Bronsted and Lewis acid zeolites.

The mechanism of CO2 reduction over Pd/Al2O3: a combined steady state isotope transient kinetic analysis (SSITKA) and operando FTIR investigation

2017 Spring Symposium

Xiang Wang, Hui Shi and János Szanyi, Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA

Abstract – Understanding the critical steps involved in the heterogeneous catalytic CO2 reduction has attracted a lot of attention recently. In order to fully understand the mechanism of this reaction the determination of both the rate-determining steps and reaction intermediates are vital. Steady-State Isotopic Transient Kinetic Analysis (SSITKA) is one of the most powerful techniques used to investigate the elementary steps under steady-state reaction conditions. This technique provides valuable information on mean resident lifetime of surface intermediates, surface concentrations of adsorbed reactant species and an upper bound of the turnover frequency. Coupling SSITKA with operando-FTIR spectroscopy allows us to discriminate between active and spectator species present on the catalytic surface under steady state reaction conditions.  In the present work operando SSITKA experiments coupled with transmission FTIR, mass spectrometry (MS) and gas chromatography (GC) were performed to probe both the chemical nature and kinetics of reactive intermediates over a Pd-Al2O3 catalysts and provide a clear mechanistic picture of the CO2 hydrogenation reaction by revealing the rate-determining steps for CH4 and CO production.

Figure 1 shows normalized real-time signals for the decay and increase of methane (a) and carbon-monoxide (b) in the effluent at 533 K reaction temperature after the feed gas was switched at 0 s from CO2/H2/Ar mixture to 13CO2/H2 mixture.  With increasing temperature, the decay of CH4 and CO get faster.  By integration under the decay curves , the mean surface-residence times CH4 and  CO), the abundance of adsorbed surface intermediates leading to CH4 and CO products  CH4 and  CO) at 533-573 K were calculated. At low temperature, CO2 methanation is slower than the reverse water-gas shift reaction, but became faster as the temperature was increased over 563 K.  The similar apparent activation energies obtained for the hydrogenation of adsorbed CO and for the formation of CH4 indicates that the hydrogenation of CO is the rate-determining step during the CO2 methanation reaction. Moreover, the similar apparent activation energies estimated for the consumption of adsorbed formates (FTIR) and for the formation of CO (MS), indicates that the H-assisted decomposition of formates is the rate determining step in the reverse water gas shift reaction.  The rate-determining step for CO formation is the conversion of adsorbed formate, while that for CH4 formation is the hydrogenation of adsorbed carbonyl. The balance of the hydrogenation kinetics between adsorbed formates and carbonyls governs the selectivities to CH4 and CO. We applied this knowledge to design catalysts and achieved high selectivities to desired products. 

Figure 1. Normalized response of (a) CH4 and 13CH4 products and (b) CO and 13CO products as functions of time.

Biography – Dr. Szanyi`s research is focused on surface science, spectroscopy and kinetic studies on heterogeneous catalytic reaction systems aimed at understanding structure-reactivity relationships. In particular, he is interested in understanding the mechanistic consequences of very high (atomic) metal dispersion on different support materials. Using a series of ensemble averaged spectroscopy methods he investigates the fundamental properties of metal atoms and small metal clusters prepared under well controlled UHV conditions. These results provide information on the energetics of the interactions between highly dispersed metals and selected probe molecules. Applying in situ RAIR spectroscopy they study the binding configurations of adsorbates to metals, and identify surface species present on the metal and support materials under elevated reactant pressures. Simultaneously, they are conducting detailed kinetics and operando spectroscopy measurements on model high surface area supported metal catalysts using flow reactors and SSITKA/FTIR/MS techniques. These measurements provide detailed kinetic information together with surface speciation that allow them to greatly enhance our mechanistic understanding of heterogeneous catalytic systems, in particular the reduction of CO2. Dr Szanyi is also involved in research related to the fundamental understanding of automotive emission control catalysis, conducting research in selective catalytic reduction of NOx on zeolite-based catalysts, low temperature NO and CO oxidation on metal oxides, and low temperatures NOx and HC storage in zeolites.

Design of complex metal/metal-oxide heterogeneous catalytic materials for energy and chemical conversion

2017 Spring Symposium

Eranda Nikolla, Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI

Abstract – Dwindling fuel resources and high levels of CO2 emissions have increased the need for renewable energy resources and more efficient energy conversion and storage systems. In this talk, some of our recent work on designing efficient (active, selective and stable) catalytic systems for energy and chemical conversions will be discussed. First, I will talk about our work on designing layered nickelate oxide electrocatalysts for electrochemical oxygen reduction and evolution reactions. These processes play an important role in fuel cells, electrolyzers and Li-air batteries. We have utilized density functional theory (DFT) calculations to identify the factors that govern the activity of nickelate oxides toward these processes. Using a reverse microemulsion approach we demonstrate an approach for synthesizing nanostructured nickelate oxide electrocatalysts with controlled surface structure. These nanostructures are thoroughly characterized using atomic-resolution high angle annular dark field (HAADF) imaging along with electron energy-loss spectroscopy (EELS) performed using an aberration corrected scanning transmission electron microscope (STEM). Controlled kinetic isotopic and electrochemical studies are used to develop structure/performance relationships to identify nickelate oxides with optimal electrocatalytic activity. Secondly, I will discuss our efforts on designing efficient catalytic systems for biomass conversion processes. Development of active and selective catalysts for biomass conversion is critical in realizing a renewable platform for fuels and chemicals. I will highlight some of our recent work on utilizing reducible metal oxide encapsulated noble metal catalytic materials to promote hydrodeoxygenation (HDO) of biomass-derived compounds. We show enhancement in HDO activity and selectivity due to the encapsulation of the metal nanoparticles by an oxide film providing high interfacial contact between the metal and metal oxide sites, and restrictive accessible conformations of aromatics on the metal surface.

Biography – Eranda Nikolla is an assistant professor in the Department of Chemical Engineering and Materials Science at Wayne State University since Fall 2011. Her research interests lie in the development of heterogeneous catalysts and electrocatalysts for chemical conversion processes and electrochemical systems (i.e., fuel cells, electrolyzers) using a combination of experimental and theoretical techniques. Dr. Nikolla received her Ph.D. in Chemical Engineering from University of Michigan in 2009 working with Prof. Suljo Linic and Prof. Johannes Schwank in the area of solid-state electrocatalysis. She conducted a two-year postdoctoral work at California Institute of Technology with Prof. Mark E. Davis prior to joining Wayne State University. At Caltech she developed expertise in synthesis and characterization of meso/microporous materials and functionalized surfaces. Dr. Nikolla is the recipient of a number of awards including the National Science Foundation CAREER Award, the Department of Energy CAREER Award, 2016 Camille Dreyfus Teacher-Scholar Award and the Young Scientist Award from the International Congress on Catalysis.

Mechanisms and Materials for Alkaline Hydrogen Electrocatalysis

2017 Spring Symposium

Maureen Tang, Chemical and Biological Engineering, Drexel University, Philadelphia, PA

Abstract – Hydrogen is a potential low cost, scalable energy storage medium for renewable electricity generation. More importantly, study of the hydrogen electrode reactions has led to the discovery of many of the fundamental concepts in electrochemistry and electrocatalysis. It has long been recognized that the reaction rates of the hydrogen oxidation and hydrogen evolution reactions (HOR and HER) are slower in basic than acidic electrolytes, even though the surface intermediate of adsorbed hydrogen is independent of solution pH. Understanding the root of this observation is critical to designing catalysts for a multitude of electrochemical reactions with relevance to energy conversion and storage. In this work, we undertake both applied and fundamental efforts to understand the mechanisms and develop low-cost, active catalysts for the hydrogen reactions in base.

In the first part of the talk, we utilize a theory-guided approach to develop nickel-silver catalysts for alkaline hydrogen evolution and oxidation. Density-functional-theory calculations predict these alloys will be active for hydrogen evolution and oxidation. To circumvent the thermodynamic insolubility of these two metals and isolate catalytic activity, we employ an uncommon physical vapor codeposition synthesis. Our measurements show that the alloy is indeed more active for hydrogen evolution than pure nickel. In the second part of the talk, we examine specifically the hypothesis that water orientation governs the rate of hydrogen adsorption and thus the overall HER/HOR kinetics by modulating the potential of zero charge of oxide supports in acid and base. Finally, we combine microkinetic modeling and single-crystal measurements to determine if adsorbed hydroxide functions as an active intermediate or spectator in the reaction. The results of these studies highlight the importance of kinetic barriers, as well as adsorption energies, and contribute to resolving a long-standing paradox in electrocatalysis and surface science.

Biography – Maureen Tang joined the faculty of Chemical and Biological Engineering at Drexel University in Fall 2014. She received her B.S. in Chemical Engineering from Carnegie Mellon University and her Ph. D. from the University of California, Berkeley. While at Berkeley, she received a NSF Graduate Research Fellowship, an NSF East Asia Pacific Summer Fellowship, and the Daniel Cubiciotti Student Award of the Electrochemical Society. Dr. Tang has completed postdoctoral work at Stanford University and research internships at Kyoto University, the University of Dortmund, and Dupont. Her research at Drexel develops materials, architectures, and fundamental insight for electrochemical energy storage and conversion.

Continuous Reactors for Homogeneous Catalysis in Pharmaceutical Manufacturing

2017 Spring Symposium

Martin D Johnson, Scott A May, Joel R Calvin, Kevin P Cole
Eli Lilly and Company, Indianapolis, IN

Abstract – Continuous flow chemistry for metal catalyzed organic reactions offers several advantages in the pharmaceutical industry. Capital cost was lower than batch for the high pressure reactors described in this presentation. The 1000 psig rated hydrogenation reactors ranged from 7 L to 360 L, and capital cost for just the reactor ranged from $4000 to $120,000. Quality assurance was higher compared to batch because the inexpensive reactors were dedicated to specific types of catalysis. For example, individual plug flow reactors (PFRs) were dedicated to Ir, some for Rh/Ru, some for Pd/Pt, and each was not used for other metals. Safety was improved compared to batch, because the continuous reactors were smaller, less reagent gas was in the reactor at any one time, and in some cases the hydrogenation reactors operated outside. A 73L PFR was used for asymmetric reduction of a tetrasubstituted enone, producing 144 kg penultimate with 95% EE. Reaction conditions were Rh(COD)2OTf, diphosphine ligand, 2000:1 S:C, 5 mol% Zn(OTf), 30% MeOH in EtOAc (10 volumes), 1000 psig H2, 1.3 molar eq H2 in flow, 70 °C, 12 h mean residence time (τ). The pipes in series PFRs proved to be superior to the coiled tubes for gas/liquid high pressure reactions in terms of scalability, gas/liquid mixing rate, % liquid filled, and inspectability. A direct asymmetric reductive amination (DARA) was run in a 32L horizontal pipes in series reactor, producing 15 kg advanced intermediate. Reaction conditions were [Ir(cod)Cl]2 and (S)-Xyl-BINAP, 4000 S:C,ketal , aminotetrazole (1.1 eq), CSA (0.02 eq), TBAI (0.01 eq), H2 (1000 psig), 12 h τ. A reductive amination was run in a 360 L vertical pipes in series reactor in GMP manufacturing, producing 2000 kg penultimate. Reaction conditions were [Ir(cod)Cl]2, no ligand, S:C 1100, 800 psig H2, 3 molar equivalents H2 in flow, 0.5 equiv TBAI wrt Ir, 1.05 eq HOAc, 1.4 eq aldehyde wrt amine, 1 volume water, 9 volumes THF, 1 volume MeTHF, 12 h τ. The reactor operated outside, and H2 was stripped from product solution before flowing back inside. A 32L oscillating flow tube reactor was used for a selective hydroformylation in which the catalyst and ligand precipitated from solution in the reactor, as they were less soluble in the product aldehyde than the methyl methacrylate reagent. Reaction conditions were (PPh)3HRhCO, S:C 1000, catalyst is dissolved in neat methyl methacrylate, 1000 psi 50:50 CO:H2, 24 h τ. The back and forth flow and custom methods of pressure control kept the reactor from fouling for the entire 314 h continuous run to produce 180 kg advanced intermediate with high selectivity of the branched aldehyde.

Biography – Martin D. Johnson works for Eli Lilly and Company in Small Molecule Design and Development.  He received his dual doctorate in chemical engineering and environmental engineering from the University of Michigan in 2000, and his undergraduate in Chemical Engineering from Virginia Tech.  Prior to joining Eli Lilly in 2005, he worked as a process research engineer at Union Carbide and The Dow Chemical Company in the Engineering Sciences and Market Development department, focusing on process development and separations.  At Eli Lilly, Dr. Johnson leads a group of engineers who focus on design and development of continuous processes.  He has applied process technologies from the chemical industry to increase efficiency, decrease waste, and increase the types of chemistries that Eli Lilly can safely scale up from research to production of small molecule pharmaceutical compounds.  Dr. Johnson’s group has used continuous reactions in the manufacture of active pharmaceutical ingredients for highly exothermic and hazardous reactions, high pressure reactions with hazardous gas reagent like hydrogenations, chemistries at extreme temperatures and pressures, and process separations including distillation, extraction, crystallization, and filtration.  Eli Lilly has implemented his continuous processes for the production of active pharmaceutical ingredient in cGMP manufacturing both internally at the Lilly facility in Ireland and externally in multiple contract manufacturing organizations.  Dr. Johnson was awarded the 2016 ACS Award for Affordable Green Chemistry, and the 2016 AIChE Award for Outstanding Contribution to QbD for Drug Substance.