Engineering Molecular Transformations over Supported Metal Catalysts for the Sustainable Conversion of Biomass-Derived Intermediates to Chemicals and Fuels

Meeting Program – October 2015

Matt Neurock
Matt Neurock
Shell Professor of Chemical Engineering and Materials Science
University of Minnesota

Abstract – Future strategies for energy production will undoubtedly require processes and materials that can efficiently convert sustainable resources such as biomass into fuels and chemicals. While nature’s enzymes elegantly integrate highly active centers together with adaptive nanoscale environments to control the catalytic transformation of molecules to specific products, they are difficult to incorporate into large scale industrial processes and limited in terms of their stability. The design of more robust heterogeneous catalytic materials that can mimic enzyme behavior, however, has been hindered by our limited understanding of how such molecular transformations proceed over inorganic materials. The tremendous advances in ab initio theoretical methods, molecular simulations and high performance computing that have occurred over the past two decades provide unprecedented ability to track these transformations and how they proceed at specific sites and within particular environments. This information together with the unique abilities to follow such transformations spectroscopically is enabling the design of unique atomic surface ensembles and nanoscale reaction environment that can efficiently catalyze specific molecular transformations. This talk discusses recent advances in computational catalysis and their application to engineering molecular transformations for the conversion of biomass into chemicals and fuels. We will discuss the active sites, mechanisms and nanoscale reaction environments involved in specific bond making and breaking reactions important in the conversion of biomass-derived intermediates into chemicals and fuels and the design of 3D environments necessary to carry out such transformations.
Biography – Matt Neurock is the Shell Professor of Chemical Engineering and Materials Science at the University of Minnesota. He received his B.S. degree in Chemical Engineering from Michigan State University and his Ph.D. from the University of Delaware in 1992. He worked as a Postdoctoral Fellow at the Eindhoven University of Technology in the Netherlands from 1992-1993 and subsequently as Visiting Scientist in the Corporate Catalysis Center at DuPont from 1993-1994. He joined the faculty in Chemical Engineering at the University of Virginia in 1995 where he held joint appointments in Chemical Engineering and Chemistry. In 2014 he moved to the University of Minnesota and is currently on the faculty in Chemical Engineering and Materials Science. He has made seminal advances to development and application of computational methods toward understanding catalytic and electrocatalytic reaction mechanisms, and the sites and environments that carry out reactions under working conditions. He has received various awards for his research in computational catalysis and molecular reaction engineering including the Robert Burwell Lectureship from the North American Catalysis Society, R.H. Wilhelm Award in Chemical Reaction Engineering from the American Institute of Chemical Engineers, Paul H. Emmett Award in Fundamental Catalysis from the North American Catalysis Society, Distinguished Visiting Professor of University of Montpellier, Eastman Chemical Lecturer at the University of California Berkeley, Richard S. H. Mah Lecturer at Northwestern University, Johansen-Crosby Lecturer at Michigan State University, NSF Career Development Award, DuPont Young Investigator Award, Ford Young Faculty Award. He has co-authored over 240 papers, two patents and two books. He is an editor for the Journal of Catalysis and serves on numerous other editorial and advisory boards.

Catalysis for renewable fuels and chemicals: Challenges today and a look into where we are going

Meeting Program – November 2015

John Holladay
John Holladay
Biomass Sector Manager, and Associate Director of the Institute for Integrated Catalysis
Pacific Northwest National Laboratory

Abstract – Renewable carbon sources, such as biomass and sugars, offer alternative starting materials for producing fuels and chemicals. However, catalysis of highly oxygenated materials, often operating in the condensed phase, present substantial challenges with catalyst deactivation due to poisoning and reactor bed/support stability. In essence, the catalysts developed within the petrochemical industry are often not suitable and new solutions are needed if we are to match the efficiency that has been born from nearly 90 years of science and technology aimed at hydrocarbon processing.
In covering challenges today we will survey two families of catalytic technologies that produce fuels—with an emphasis on distillates and mid-distillates and chemical products. These technologies will cover (i) upgrading of oxygenates (from alcohols to complex bio-oils) and (ii) catalysis of fermentation derived molecules that have been minimally processed. The primary focus will be on problems and specific solutions that allowed long term, stable and efficient operation under continuous reaction conditions suitable for industry.
In part 2 of the lecture we will take a forward look toward where we would like to move the state of catalyst technology to allow processing of a broader range of carbon from waste resources at the (small) size of the point source while keeping capital and operating cost low. Such feedstocks include gaseous streams, such as CO-rich off gas; wet streams from food processing and waste water sludges; as well as dry streams from agriculture and forest residues or municipal solid waste.
Biography – John Holladay joined the Pacific Northwest National Laboratory (PNNL) in 2001 after working for five years at Union Carbide in South Charleston, WV. John currently serves as the Biomass Sector Manager at PNNL, where he is responsible for shaping PNNL’s strategy and vision for renewable fuels and chemicals. The program focuses on multiple areas including: developing cost-effective catalysts for renewable carbon conversion, learning from the efficiency that fungi offers for naturally processing biomass, and understanding alternative means for producing biomass in waste streams that are wet/dry or gaseous. He facilitates PNNL’s collaboration with others in academia, industry and government to advance the nation’s biofuels research. He served as Chief Scientific Officer for the National Advanced Biofuels Consortium, Chief Operations Officer for the National Alliance for Biofuels and Bioproducts and is currently an Associate Director of the Institute for Integrated Catalysis at PNNL.

Catalysis – An Indispensable Tool

Meeting Program – September 2015

Sourav Sengupta
Sourav Sengupta
Molecular Sciences, CR&D
E. I. DuPont de Nemours & Co
Wilmington, DE
Abstract – In the past three decades, there has been a concerted effort in the chemical, agrochemical, pharmaceutical, nutraceutical, and petroleum industries to design cost-advantaged, inherently safer, sustainable, and environmentally-friendly processes. Catalysis plays a crucial role in improving process efficiencies and process intensification leading to increased atom utilization, reduced by-product formation, cheaper process, and lower capital investment. Also, there is an increasing interest in using renewably-sourced feedstocks for the production of fuels, chemicals, and advanced materials due to fluctuations in petroleum prices, limited availability of petroleum resources, and increasing consumer consciousness about sustainable processes.
Although catalysis is a major tour-de-force in driving this efficacious and green chemistry revolution, the role of reaction engineering, reactor design, process development, and optimum operating conditions cannot be underestimated. Some of the fundamental concepts of catalysis will be discussed and linked to chemical processes of industrial relevance. Specifically, the role of science and engineering in industrial catalysis will be illustrated with particular emphasis on catalyst evaluation, process optimization, catalyst deactivation, and reactor design associated with industrial processes. Case studies will include hydrogenation reactions using supported base metal and precious metal catalysts and solid acid catalyzed reactions, including the hydrogenation of hexafluoroacetone and catmint oil, and dehydration of xylose.
Biography – Dr. Sourav K. Sengupta is a Research Fellow in the Molecular Sciences Division (Central Research & Development Department) of E. I. DuPont de Nemours & Co. He received his PhD degree in Chemical Engineering from the University of Delaware in 1991. Immediately after completing his PhD, Dr. Sengupta joined the DuPont Company and was placed on loan to Conoco where he developed novel pathways for the oxidative desulfurization of gasoline and qualified new hydrodesulfurization and FCC catalysts. Shortly afterwards, he was transferred to the Corporate Catalysis Center (CR&D). At CR&D, he worked on solid acid, solid base, and hydrogenation catalysis programs and made important contributions to a number of Strategic Business Unit (SBUs).
Dr. Sengupta spent several years at DuPont’s Nylon business unit, where he worked on a number of commercial processes and research programs, including low-pressure and high-pressure ADN hydrogenation, hydrogen cyanide synthesis by Andrussow and induction-heating processes, and nitrous oxide destruction catalyst technology.
When DuPont sold their Nylon, polyester, and Lycra businesses to Koch Industries, Dr. Sengupta joined Invista, a wholly-owned subsidiary of Koch Industries, where his work involved investigating the technical and economic feasibility of caprolactam commercialization.
After a short stint at Invista, Dr. Sengupta came back to DuPont, and joined their Chemical Solutions Enterprise (DCSE) as a manufacturing technical chemist at Chambers Works in New Jersey. His responsibility covered 42 different specialty chemicals. There he worked with a team of experts to design, develop, and commercialize a novel hydrogenation process for the production of hexafluoroisopropanol (HFIP) and hexafluoroacetone (HFA) recovery process. He was also involved in the commercialization of a number of Capstone products. In 2009, he started up a Process Development Center for DCSE at the Experimental Station. In 2011, he moved back to CR&D and has been working on a number of R&D programs on using renewable feedstock to manufacture chemicals and materials and new catalyst development.
Dr. Sengupta’s expertise is in the area of catalysis, reaction engineering and reactor analysis, and process development. He has over 65 US patents, publications, and presentations to his credit.

The Design of New Catalysts for Biomass Conversion with Atomic Layer Deposition

Meeting Program – April 2015

George Huber
Department of Chemical and Biological Engineering
University of Wisconsin, Madison, WI

The objective of the Huber research group is to develop new catalytic processes and catalytic materials for the production of renewable fuels and chemicals from biomass, solar energy, and natural gas resources. We use a wide range of modern chemical engineering tools to design and optimize these clean technologies including: heterogeneous catalysis, kinetic modeling, reaction engineering, spectroscopy, analytical chemistry, nanotechnology, catalyst synthesis, conceptual process design, and theoretical chemistry. In this presentation we will first discuss the hydrodeoxygenation of biomass into different fuels and chemicals. In addition we can use HDO to easily produce new classes molecules that are not currently produced from petroleum feedstocks. Hydrodeoxygenation (HDO) is a platform technology used to convert liquid biomass feedstocks (including aqueous carbohydrates, pyrolysis oils, and aqueous enzymatic products) into alkanes, alcohols and polyols. In this process the biomass feed reacts with hydrogen to produce water and a deoxygenated product using a bifunctional catalyst that contains both metal and acid sites. The challenge with HDO is to selectively produce targeted products that can be used as fuel blendstocks or chemicals and to decrease the hydrogen consumption. We will discuss how different biomass based feedstocks can be converted into fuels or chemicals by HDO. We will outline the fundamental catalytic chemistry and the scientific challenges. We will then discuss how ALD can be used to design improved catalytic materials.

Atomic layer deposition (ALD) has emerged as a tool for the atomically precise design and synthesis of catalytic materials. We discuss examples where the atomic precision has been used to elucidate reaction mechanisms and catalyst structure-property relationships by creating materials with a controlled distribution of size, composition, and active site. We highlight ways ALD has been utilized to design catalysts with improved activity, selectivity, and stability under a variety of conditions (e.g., high temperature, gas- and liquid-phase, and corrosive environments). In addition, due to the flexibility and control of structure and composition, ALD can create myriad catalytic structures (e.g., high surface area oxides, metal nanoparticles, bimetallic nanoparticles, bifunctional catalysts, controlled micro-environments, etc.) that consequently possess applicability for a wide-ranging number of chemical reactions (e.g., CO2 conversion, electrocatalysis, photocatalytic and thermal water splitting, methane conversion, ethane and propane dehydrogenation, and biomass conversion). Finally, the outlook for ALD-derived catalytic materials is discussed with emphasis on the pending challenges as well as areas of significant potential for building scientific insight and achieving practical impacts.

George Huber
George W. Huber is a Professor of Chemical Engineering at University of Wisconsin-Madison. His research focus is on developing new catalytic processes for the production of renewable liquid fuels and chemicals.

George is one of the most highly cited young scholars in the chemical sciences being cited over 3,200 times in 2014 and over 14,000 times in his career. He has authored over 100 peer-reviewed publications including three publications in Science. Patents and technologies he has helped develop have been licensed by three different companies. He has received several awards including the NSF CAREER award, the Dreyfus Teacher-Scholar award, fellow of the Royal Society of Chemistry, and the outstanding young faculty award (2010) by the college of engineering at UMass-Amherst. He has been named one of the top 100 people in bioenergy by Biofuels Digest for the past 3 years. He is co-founder of Anellotech a biochemical company focused on commercializing, catalytic fast pyrolysis, a technology to produce renewable aromatics from biomass. George serves on the editorial board of Energy and Environmental Science, ChemCatChem, and The Catalyst Review. In June 2007, he chaired a NSF and DOE funded workshop entitled: Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels (

George did a post-doctoral stay with Avelino Corma at the Technical Chemical Institute at the Polytechnical University of Valencia, Spain (UPV-CSIC) where he studied bio-fuels production using petroleum refining technologies. He obtained his Ph.D. in Chemical Engineering from University of Wisconsin-Madison (2005). He obtained his B.S. (1999) and M.S.(2000) degrees in Chemical Engineering from Brigham Young University.

DFT Investigation of Hydrogenation and Dehydrogenation Reactions on Binary Metal Alloys: Effect of Surface Ensembles and Composition

Meeting Program – March 2015

Fuat E Celik
Department of Chemical and Biomolecular Engineering
Rutgers, The State University of New Jersey

Fuat Celik
In supported metal catalysts, the tradeoff between activity and selectivity presents an important challenge for catalyst design. By allowing two dissimilar metals, we can attempt to tune the selectivity of the catalyst by enhancing bond-formation and desorption rates through the addition of a less-reactive element, while maintain high bond dissociation activity from the more active metal. The resulting catalyst properties depend strongly on the catalyst composition and ratio of the two metals (electronic effect), but may also depend on the local structure of surface ensembles of the alloy components (geometric effect). In this talk we will explore two examples of binary alloys where surface composition and geometry play an important role in determining the selectivity of the catalyst through density functional theory (DFT).

In the first example, we have examined the effect of platinum tin alloy structure and composition on the kinetics and thermodynamics of dehydrogenation and coke formation pathways during light alkane dehydrogenation. Light alkane dehydrogenation to olefins can add significant value to hydrocarbon processes that generate ethane and propane by converting low value commodity fuels to high-value chemical and polymer precursors. Supported Pt catalysts are known to be active but show significant coke formation and deactivation, which can be alleviated by alloying with Sn and other main group elements. We aim to understand how the structure and composition of these alloys affect their ability to suppress coke formation. We investigate the potential energy surfaces from ethane along the desired pathway to ethene, and along the undesired pathways towards surface carbon/coke. The effect of Pt/Sn ratio and surface geometry is investigated. As compared to pure Pt, bond scission is more difficult on the alloys and desorption is more facile, and both effects are enhanced as three-fold hollow sites consisting of only Pt atoms are eliminated.

In the second example, we evaluate Au/Ni near-surface alloys as potential oxygen reduction catalysts for the direct synthesis of hydrogen peroxide from O2 and H2, thereby avoiding the current anthraquinone process. While Au may have higher O-H bond formation activity, it is a poor O2-dissociation catalyst, and likewise Ni is very effective at O2-dissociation but not oxygen hydrogenation. Alloying Au with Ni(111) lowers H2 dissociation barrier while keeping the O2 dissociation barrier large relative to O2 hydrogenation. Desorption of H2O2 is similarly competitive with H2O2 dissociation on alloy surfaces. However, the selectivity for the OOH radical remains a challenge, with barrierless O-O bond dissociation and large (1.3 eV) hydrogenation barriers. We further investigate how the Au/Ni surface may rearrange itself to regenerate three-fold hollows of Ni atoms in the presence of strongly adsorbing surface species.

Methane Conversion to Methanol on Copper Containing Small Pore Zeolites

Meeting Program – February 2015

Bahar Ipek
Department of Chemical and Biomolecular Engineering
University of Delaware

Bahar Ipek
Methanotrophic bacteria containing particular methane monooxygenase (pMMO), a Cu-containing enzyme, or soluble methane monooxygenase (sMMO), an iron-metalloenzyme can oxidize methane to methanol selectively at ambient conditions 1. The zeolite Cu-ZSM-5 was reported to activate the methane C-H bond—with a homolytic bond dissociation energy of 104 kcal/mol— at temperatures as low as 120 °C 2 after pretreatment in O2 3. The reactive copper species are believed to contain extra-lattice oxygen, and in the case of Cu-ZSM-5, to be a mono-μ-oxo-dicopper complex ([Cu—O—Cu]2+) 4. Although a correlation was found between the concentration of mono-μ-oxo-dicopper species and the amount of methanol produced by Cu-ZSM-5 5, no such correlation was found for other zeolites that produce methanol such as Cu-mordenite and Cu-ferrierite 2. We have recently showed methanol production on copper (II) exchanged small pore zeolites including SSZ-13 (CHA), SSZ-16 (AFX) and SSZ-39 (AEI) with yields as high as 39 μmol CH3OH/g and CH3OH/Cu ratios up to 0.09 (the largest reported to date).6 Here, copper species in these small pore zeolites were investigated with UV–vis and Raman spectroscopy after O2-treatment at a temperature of 450 °C. No evidence of mono-μ-oxo-dicopper species was found in the spectra of Cu-SSZ-13,Cu-SSZ-16 and Cu-SSZ-39 6, however Cu—Oextralattice vibrations at 574 cm-1 were detected in Raman spectra of Cu-SSZ-13 and Cu-SSZ-39 zeolites which is indicative of a different CuxOy active species responsible for methanol production in small pore zeolites.

1. Hanson, R. S.; Hanson, T. E., Methanotrophic Bacteria. Microbiological Reviews
1996, 60, 439-471.
2. Smeets, P. J.; Groothaert, M. H.; Schoonheydt, R. A., Cu based zeolites: A UV–vis
study of the active site in the selective methane oxidation at low temperatures.
Catal. Today 2005, 110 (3-4), 303-309.
3. Groothaert, M. H.; Smeets, P. J.; Sels, B. F.; Jacobs, P. A.; Schoonheydt, R. A.,
Selective Oxidation of Methane by the Bis(mu-oxo)dicopper Core Stabilized on
ZSM-5 and Mordenite Zeolites. Journal of American Chemical Society 2005, 127,
4. Woertink, J. S.; Smeets, P. J.; Groothaert, M. H.; Vance, M. A.; Sels, B. F.;
Schoonheydt, R. A.; Solomon, E. I., A [Cu2O]2+ core in Cu-ZSM-5, the active site in
the oxidation of methane to methanol. Proceedings of the National Academy of
Sciences of the United States of America 2009, 106 (45), 18908-13.
5. Beznis, N. V.; Weckhuysen, B. M.; Bitter, J. H., Cu-ZSM-5 Zeolites for the Formation
of Methanol from Methane and Oxygen: Probing the Active Sites and Spectator
Species. Catal. Lett. 2010, 138 (1-2), 14-22.
6. Wulfers, M. J.; Teketel, S.; Ipek, B.; Lobo, R. F., Conversion of Methane to Methanol
on Copper Containing Small Pore Zeolites and Zeotypes. Chem Commun 2015, xx,

Bridging Heterogeneous Catalysis and Electro-catalysis: Catalytic Reactions Involving Oxygen

Meeting Program – February 2015

Dr. Umit S. Ozkan
Department of Chemical and Biomolecular Engineering
The Ohio State University

Umit Ozkan
Catalytic reactions that involve oxygen can be found in a large number of processes, including those in energy-related applications, in emission control and in processes important for the chemical industry. Whether the catalytic reaction is an oxygen insertion step as in a selective oxidation reaction, or an oxygen removal step as in a hydrodeoxygenation reaction, oxygen has proven to be a very challenging component, often determining the selectivity of the reaction. Some examples from our laboratories that bridge catalysis and electro-catalysis will be discussed, ranging from oxidative dehydrogenation of alkanes to oxygen reduction reaction in fuel cells.