Author Archives: Carl Menning

Nominees For 2018-2019 CCP Officers

Nominees for Chair Elect

Marat Orazov

Marat Orazov obtained his B.S. degree in Chemical Engineering in 2012, at the University of California, Berkeley, having performed undergraduate research in the labs of Profs. Alexander Katz and David B. Graves. Then, under the guidance of Prof. Mark E. Davis, he pursued a Ph.D. in Chemical Engineering at Caltech, where he studied a number of catalytic systems pertaining to the synthesis of valuable chemicals from biomass. In the fall of 2016, Dr. Orazov started his postdoctoral research with Prof. Thomas F. Jaramillo, at Stanford, developing thermocatalytic systems for the synthesis of higher alcohols and cathode electrocatalysts for hydrogen fuel cells. In the summer of 2018, he will join the faculty as an Assistant Professor, at the Department of Chemical & Biomolecular Engineering, at the University of Delaware. He aims to study and develop materials and coupled catalytic systems for the renewable generation and storage of energy, and chemical synthesis, with particular interest in microporous materials and electrochemistry.

Jacob Dickinson

Jake started at DuPont 2014. He has worked on a variety of projects including the conversion of non-edible biomass into an intermediate for renewable monomers, development of thermoplastic composites for compressed hydrogen storage vessels, and, most recently, on monomer and polymer process development.

Prior to joining DuPont, Jake attended Hope College and graduated with a B.S. in Chemical Engineering, and then went on to the University of Michigan and graduated with a Ph.D. in Chemical Engineering. The general focus of his thesis was the hydrodeoxygenation of phenols in supercritical water. A major contribution of his thesis was the synthesis and use of a Cu-doped Raney Ni catalyst that contained tunable HDO and gasification activity depending on the Cu content of the catalyst.

Jake served as the Membership Director during the 2016-17 CCP season and hopes to continue serving the catalysis community.

Nominees for Treasurer

Lifeng Wang

Lifeng Wang is a research chemist in Zeolyst International and his research work is focused on developing various zeolite catalysts for automotive applications. He received his BS and PhD in Chemistry from Jilin University, China, where his research was focused on design and synthesis of novel sorbents and catalysts including silicas, carbons and zeolites. Lifeng has been an active member of the Catalysis Club of Philadelphia since 2014.

Istvan Halasz

Istvan is Principal Chemist at the Research & Development Center of PQ Corporation, studying the structure and properties of silica-derivatives. Prior to this he studied catalytic processes and superconducting ceramics partly at US universities and partly at the Central Chemistry Institute of the Hungarian Academy of Sciences. From this latter institution he obtained a Ph. D. equivalent degree and also holds a doctorate degree from the Lajos Kossuth University (Hungary). In the initial 12 years of his research carrier he worked at the Hungarian Hydrocarbon Institute, developing and scaling-up efficient patented processes for pharmaceutical, fine chemical and petrochemical industries along with performing fundamental studies in acid-base catalysis. He served as president and chair in various scientific organizations, edited one book, authored circa 125 book chapters, papers and patents and held 90+ conference presentations.

Nominees for Director (Poster, Membership and Sponsorship)

Runbo Li

Runbo Li obtained her Ph.D. in Analytical Chemistry from Drexel University in USA. In her thesis, she studied different methods for preparing samples for analysis by MALDI TOFMS and applied these methods to quantify proteins. At PQ R&D, she has focused on analytical method development and characterization research related to silicates, glass beads, amorphous silica gel and zeolites. She has published 18 papers.

Nicholas McNamara

Nicholas McNamara attained a B.S. (2009) and M.S. (2011) from the University of Dayton where he carried out research on the sonochemical synthesis and characterization of carbon-supported metal nanoparticles. He then attended the University of Notre Dame where his graduate research was supported by the Patrick and Jana Eilers Graduate Student Fellowship for Energy Related Research. In his graduate research, he studied the synthesis, characterization, and utilization of metal-organic frameworks (MOFs) and MOF-templated materials as oxidative desulfurization catalysts. He earned his PhD in 2015 under the direction of Prof. Jason Hicks. He began his industrial research career in 2016 as a staff scientist in the Clean Air division of Johnson Matthey. His current research focuses on the design of new materials for targeted emissions control applications and the determination of structure-property relationships.

Bill Borghard

Currently, Bill is a consultant in the area of catalysis. In particular, he is the industrial liaison for the Rutgers Catalyst Manufacturing Consortium, based in the Chemical and Biochemical Engineering Department at Rutgers University. He is also on the Advisory Board for the Catalysis Center for Energy Innovation (CCEI), based at the University of Delaware.

Bill retired from ExxonMobil in 2013 after 32 years with the company. He started at the Mobil Paulsboro Lab in 1980 investigating Fischer-Tropsch/ZSM-5 two-stage wax upgrading. In 1982, Bill transferred to Mobil’s lab in Princeton working in exploratory research and lab automation. In 1992, Bill returned to Paulsboro, where he had assignments in reforming, light gas upgrading, and catalyst characterization. Subsequently, he moved to the Clinton labs of ExxonMobil, where he led a number of major R&D projects, including GTL catalyst development, novel diesel catalysts, Algae BioFuels, and resid upgrading. Bill is an inventor or co-inventor on 24 U.S. patents.

Prior to joining Mobil, Bill graduated from Stanford University with a Ph.D. in chemical engineering under the tutelage of Michel Boudart. He also obtained and M.S. and B.S. in chemical engineering from the University of Connecticut where he studied under C.O. Bennett. He volunteers for Seeds of Hope Ministries (Camden, NJ).

Jim Hughes

Jim Hughes completed obtained his bachelors of Science from the University of California, Los Angeles in Chemistry (UCLA). After graduation he spent two years working in the Catalysis Development group at Chevron’s R&D center in Richmond California working on heterogeneous catalyst development. Afterwards Jim left Chevron to pursue his Ph.D. under the guidance of Alexandra Navrotsky at The University of California, Davis. Jim’s Ph.D. was the study of the Thermodynamics of Metal-Organic Frameworks. During his Ph.D. Jim was awarded a NSF-EASPI fellowship. Currently Jim Is a Senior Research Chemist with Zeolyst International, working on pilot scale synthesis and commercial production of zeolite molecular sieves.

Renewable Isoprene By Sequential Hydrogenation of Itaconic Acid and Dehydra-Decyclization of 3-Methyl-Tetrahydrofuran

2018 Spring Symposium

Omar Abdelrahman, Post-Doc, Paul Dauenhauer Group, Department of Chemical Engineering & Material Science, University of Minnesota, 421 Washington Ave. SE, Minneapolis, MN 55455

Abstract – The catalytic conversion of biomass-derived feedstocks to value added chemicals is an important challenge to alleviate the dependence on petroleum-based resources. To accomplish this, the inherently high oxygen content of biomass compounds, such as that of lignocellulosic biomass, requires significant reduction via hydrodeoxygenation strategies. The unsaturated carboxylic acid itaconic acid (IA) can be produced from biomass via fermentation pathways, for example. A pathway of interest is the conversion of IA to isoprene, facilitating the renewable production of an industrially relevant diolefin. IA can be successively hydrogenated to yield 3-methyl tetrahydrofuran (3-MTHF), in a one-pot cascade reaction, where a Pd-Re bimetallic catalyst results in an 80% yield to 3-MTHF. The 3-MTHF can then be converted to isoprene, and other pentadienes, through an acid catalyzed vapor-phase dehydra-decyclization. Multiple solid acid catalysts, including aluminosilicates, metal oxides and phosphorous modified zeolites, were screened for the dehydra-decyclization step. A new class of catalytic materials, all silicon
phosphorous containing zeolites, were found to be the most selective (70% isoprene and 20% pentadienes), where the major side reaction involved is a retro-prins condensation of 3-MTHF to butane and formaldehyde. Through kinetic studies, an investigation into the effect of Brønsted acid strength, pore size and operating conditions on the selectivity to isoprene are discussed. The prospect of applying this dehydra-decyclization strategy to other saturated cyclic ethers will also be discussed, which enables the production of other diolefin molecules of interest such as butadiene and linear pentadienes.

[1] Abdelrahman, O. A.; Park, D. S.; Vinter, K. P.; Spanjers, C. S.; Ren, L.; Cho, H. J.; Zhang, K.; Fan, W.; Tsapatsis, M.; Dauenhauer, P. J. ACS Catal. 2017, 7, 1428-1431.

Using Water as a Co-catalyst in Heterogeneous Catalysis to Improve Activity and Selectivity

2018 Spring Symposium

Lars C. Grabow, Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX 77204-4004, USA

Abstract – “What happens when you add water?” is possibly the most frequently asked question after presentations in heterogeneous catalysis. In this talk, I will demonstrate that this question is indeed paramount and that the presence of even minute amounts of water can drastically change reaction rates and product selectivities. Examples include water-mediated proton hopping across a metal-oxide surface, oxidation of carbon monoxide at the gold/titania interface, and hydrodeoxygenation of phenolic compounds over titania supported ruthenium catalysts. Together, these examples demonstrate that water can act as co-catalyst in a variety of catalytic reactions and by varying the amount of water it may be possible to tune reaction rates and product selectivity.

Selective Catalytic Oxidation of Alcohols over Supported Metal Nanoparticles and Atomically-Dispersed Metal Cations

2018 Spring Symposium

Robert J. Davis, Department of Chemical Engineering, University of Virginia, Charlottesville, VA, USA

Abstract – Selective oxidation of alcohols to carbonyl compounds is an important reaction in organic synthesis and will likely play a significant role in the development of value-added chemicals from biomass. The industrial application of a precious metal catalyst such as Pt, however, can be hindered by deactivation and high price. We have therefore explored the mode of deactivation during alcohol oxidation on Pt by in-situ spectroscopy and studied the role of various promoters on catalyst performance. Results confirm that slow decarbonylation of product aldehyde deposited unsaturated hydrocarbon on the surface that blocked access to the active sites. Addition of Bi as a promoter did not prevent the decarbonylation side reaction, but instead enhanced the activation of dioxygen during the catalytic cycle. In an effort to avoid the use of precious metals altogether, the oxidation of alcohols over atomically-dispersed, non-precious metal cations (Fe, Cu, and Co) located in a nitrogen-doped carbon matrix was demonstrated. Extensive characterization of these non-precious metal catalysts revealed important insights into the oxidation mechanism and stability of this new class of atomically-dispersed metal catalyst.

Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration and Phase Transformation Methods

2018 Spring Symposium

Jennifer D. Lee, Ph.D. Candidate, Christopher B. Murray Group, Department of Chemistry, University of Pennsylvania

Abstract – The proton exchange membrane fuel cell (PEMFC) is a critical technology to enhance the clean, sustainable production and usage of energy, but practical application remains challenging because of the high cost and low durability of the cathode catalysts that perform oxygen reduction reaction (ORR). Efforts have been placed on the study of introducing first-row transition metals in Pt-M alloys to reduce the Pt loading and modulate geometric, structural and electronic effects. To further improve the ORR reaction rate and catalysts stability, alloys that adopt an intermetallic structure, especially the tetragonal L10-PtM phase, has been one of the most promising materials. In this contribution, monodisperse PtCo nanocrystals (NCs) with well-defined size and Co composition are synthesized via solvothermal methods. The transformation from face-centered cubic (fcc) to ordered face-centered tetragonal (fct) structure was achieved via thermal annealing. Depending on the selection of transformation methods, different degrees of ordering were introduced and further correlated with their ORR performance. A detailed study of the annealing temperature and composition dependent degree of ordering is also highlighted. This work provides the insight of discovering the optimal spatial distributions of the elements at the atomic level to achieve enhanced ORR activity and stability.

Commercial Perspective of Alternative Routes to Acrylic Acid Monomer

2018 Spring Symposium

Jinsuo Xu, The Dow Chemical Company, 400 Arcola Rd, Collegeville, PA 19426

Abstract – Acrylic acid and corresponding acrylates are major monomers for a variety of functional polymers used broadly in our daily life such as coating, sealant, and personal care. The two-stage selective oxidation of propylene to acrolein and then to acrylic acid was first commercialized in early 70s and quickly became the dominant route to acrylic acid. Driven by feedstock cost or availability or sustainability, significant efforts from both industry and academia were devoted to developing alternative routes to acrylic acid. Catalyst plays critical role in the key step of transforming different raw material into product effectively, for example, mixed metal oxides MoVTeNbOx in propane selective oxidation, solid acids in dehydration of glycerin or 3-HP, and various oxides in aldol condensation of acetic acid and formaldehyde. This presentation will discuss the progress of these major routes, the challenges towards commercialization, and potential solutions.

Mechanisms, active intermediates, and descriptors for epoxidation rates and selectivities on dispersed early transition metals

2018 Spring Symposium

Daniel Bregante, Alayna Johnson, Ami Patel, David Flaherty, Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana-Champaign

Abstract – Early transition metal atoms (groups IV-VI) dispersed on silica and substituted into zeolites effectively catalyze the epoxidation of alkenes with hydrogen peroxide or alkyl peroxide reactants, yet the underlying properties that determine the selectivities and turnover rates of these catalysts are unclear. Here, a combination of kinetic, thermodynamic, and in situ spectroscopic measurements show that when group IV – VI transition metals are dispersed on silica or substituted into zeolite *BEA, the metals that form the most electrophilic sites give greater selectivities and rates for the desired epoxidation pathway and present smaller enthalpic barriers for both epoxidation and H2O2 decomposition reactions.

In situ UV–vis spectroscopy shows that these group IV and V materials activate H2O2 to form pools of hydroperoxide and peroxide intermediates. Time-resolved UV–vis measurements and the isomeric distributions of cis-stilbene epoxidation products suggest that the active species for epoxidations on group IV and V transition metals are only M-OOH and M-(O2)2– species, respectively. Mechanistic interpretations of turnover rates show that these group IV and V materials catalyze epoxidations (e.g., of cyclohexene, styrene, and 1-octene) and H2O2 decomposition through similar mechanisms that involve the irreversible activation of coordinated H2O2 followed by reaction with an olefin or H2O2. Epoxidation rates and selectivities vary over five- and two-orders of magnitude, respectively, among these catalysts and depend exponentially on both the energy for ligand-to-metal charge transfer (LMCT) and chemical probes of the difference in Lewis acid strength between metal centers. Together, these observations show that more electrophilic active-oxygen species (i.e., lower-energy LMCT) are more reactive and selective for epoxidations of electron-rich olefins. The micropores of zeolites about active sites can serve to preferentially stabilize reactive states that lead to epoxidations by changing the mean diameter of the pore or the density of nearby silanol groups. Consequently, these properties provide opportunities to increase rates of epoxide formation over that within mesoporous silicas. Consistently, H2O2 decomposition rates possess a weaker dependence on the electrophilicity of the active sites and the surrounding pore environment, which indicates that catalysts with both greater rates and selectivities may be designed following these structure-function relationships.